- Email: [email protected]
N.M.R. Spectroscopy of Fluorinated Monosaccharides*
ADVANCES IN CARBOHYDRATE CHEMISTRY AND BIOCHEMISTRY, VOL. 46
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES* BY RENB CSUK**AND BRIGITTEI. GLANZER** Instirute of Organic Chemistry, Technical University of Graz, Graz, Austria I. Introduction ............................................................ 11. Spectroscopy of Fluorinated Monosaccharides ............................. 1. IH-N.m.r. Spectroscopy .............................................. 2. W-N.m.r. Spectroscopy .............................................. 3. I9F-N.m.r. Spectroscopy .............................................. 4. Other Nuclei.. ....................................................... 111. Tables ................................................................. 1. Guide to Tables.. .................................................... 2. Tables .............................................................. Addendum .............................................................
73 74 75 77 78 80 80 80 82 33 1
I. INTRODUCTION Within the past two decades, the importance of nuclear magnetic resonance (n.m.r.) spectroscopy has enlarged tremendously. Its advantages over other methods in the structural and conformational analysis of such complex molecules as natural products , I and particularly with regard to the still-increasing importance of medical investigations2 using n.m.r. techniques, is abundantly evident. Because destruction of the sample is avoided, different n.m.r. experiments can be performed repeatedly, and
* The authors thank Dr. Karl Dax, Institute of Organic Chemistry, Technical University,
Graz,for suggesting that we make such a compilation and for pointing out its potential
practical use. ** Present address: Organisch-Chemisches Institut der Universitat, Winterthurer Strasse 190, CH-8057, Zurich, Switzerland. (1) G. Govil and R. V. Hosur, in E. Diehl, E. Fluck, and R. Kosfeld (Eds.), NMR- Basic
Principles and Progress, Vol. 20, Springer Verlag, Berlin, 1982. (2) K. Roth, NMR-Tomography and -Spectroscopy in Medicine, Springer Verlag, Berlin, 1984. 73 Copyright 0 1988 by Academic Press, Inc. All rights of reproduction in any form reserved.
RENE CSUK AND BRIGITTE I. GLANZER
74
analysis of the spectra is usually convenient, simple, and fast.3This methodology is exceptionally free from artifacts, thus allowing detailed analysis of conformational behavior in solution in comparison with the conformation in the solid state (obtained from X-ray analysis or from a n.m.r. spectrum of the solid4). 11. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
Application of 1H-n.m.r. spectroscopy to such complex molecules as carbohydrate^^.^ in general, and fluorinated monosaccharides7 in particular, soon showed the limits of this methodology, and prompted the development of modifications. Double- and triple-resonance techniques5q6and isotopic labelling of compounds, together with the use of Fourier-transform spectroscopy at very high field-strength now allows acquisition of high-resolution, n.m.r. spectra. Further progress followed the application of two-dimensional* n.m.r. techniques in the carbohydrate field.9 Because of these great improvements, all magnetic nuclei can now be used in n.m.r. analysis of fluorinated monosaccharides,1° including 'H, 13C, 15N,and 19F.Table I gives the relevant, spectroscopic data for these nuclei. TABLEI Comparison of the Relevant Parameters of Different NucleP5 Nuclei
Spin
Natural abundance
H
112 1/2 1/2 112
99.98 1.11 0.37 100
Sensitivity Gyromagnetic Relative Absolute" Rangeb ratio FrequencyC ~~
c
N F
loo0 15.9 1.04 830
~~~
lo00 0.18 0.004
830
20 650 1000 800
2.793 0.702 0.283 2.627
100 25.14 10.13 94.08
a Relative sensitivity: at constant field for equal number of nuclei; absolute intensity: product of relative sensitivity and natural abundance. In parts per million (p.p.m.). For a field strength of 2.3480 tesla.
(3) E. D. Bishop, Annu. Rep. NMR Spectrosc., 1 (1968) 91-134. (4) M. Mehring, Principles of High Resolution NMR in Solids, 2nd edn., Springer Verlag, Berlin, 1983. (5) T. D. Inch, Annu. Rep. NMR Spectrosc., JA (1972) 305-352. (6) L.D. Hall, in W. Pigman and D. Horton (Eds.), The Carbohydrates; Chemistry and Biochemistry, 2nd edn., Vol. IB, Academic Press, New York, 1980, pp. 1299-1326. (7) P. J. Card, J . Carbohydr. Chem., 4 (1985) 451-487. (8) A. Bax, Two-Dimensional Nuclear Magnetic Resonance in Liquids, Reidel, Dordrecht, 1982. (9) L. D. Hall and S. Sukumar, J . Am. Chem. SOC.,101 (1979) 3120-3121. (10) A. A. E. Penglis, Adv. Carbohydr. Chem. Biochem., 38 (1981) 195-285.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
75
1. 'H-N.m.r. Spectroscopy
a. Chemical Shifts.-Introduction of a fluorine atom into an organic molecule causes a significant shift to low-field of the signals of the geminal hydrogen atoms. However, the practical use of this effect, and its interpretation in terms of structure and conformation, remain small.
b. lH-19F Coupling Constants.-The 'H-19F spin-spin coupling is influenced by steric and electronic influences of substituents, both in close proximity to, or remote from, the coupling nuclei. The stereospecific dependences of fluorine-proton couplings compared to the corresponding 'H-lH couplings are much more sensitive to the steric environment, and the coupling constants are of much greater magnitude. Because IH-19F coupling-constants can be readily extracted from the 19F spectrum without interference of proton-proton coupling-patterns, this additional information facilitates even the interpretation of the proton spectra without the need for fluorine decoupling experiments. Geminal Coupling, 3 ('H, 19F). The sign of geminal coupling constants has been determined" and shown to be absolutely positiveI2 and to occur in secondary, carbohydrate-derived pyranoid derivatives in a range lying between 49 and 59 Hertz (Hz), whereas the furanoid counterparts show coupling of 49-66 Hz; where fluorine is attached to sp-hybridized carbon atoms, couplings of some 80 Hz may be observed. An empirical approachI3 for estimating geminal coupling-constants has been described for a limited class of compounds. Irrespective of whether fluorine is axially or equatorially oriented, an increase (-3 Hz) in 2J results upon changing the vicinal substituent from the axial (a) to the equatorial (e) orientation, whereas changing the fluorine atom from equatorial to axial has little or no effect. An exception to the latter occurs in cases where the substituent is a ring-oxygen or -sulfur atom. Vicinal Coupling, 3J (lH, 19F). The signs14 of vicinal couplings were found to be absolutely po~itive,'~ and their angular dependence parallels*0 ranging between 0 and that of proton-proton coupling-c~nstants,~~J~ (11) L. D. Hall, R. N. Johnson, A. B. Foster, and J. H. Westwood, Can. J . Chem., 49 (1971) 236-240. (12) A. D. Barford, A. B. Foster, J. H. Westwood, L. D. Hall, and R. N. Johnson, Carbohydr. Res., 19 (1971) 49-61. (13) L. Phillips and V. Wray, J . Chem. Soc., Perkin Trans. 2 , (1974) 928-933. (14) L. D. Hall and J. F. Manville, Chem. Znd. (London), (1967) 468-469. (15) L. D. Hall and J. F. Manville, Carbohydr. Res., 9 (1969) 11-19. (16) A. Gaudemer, in H. B. Kagan (Ed.), Stereochernistty: Fundamentals and Methods, Vol. 1, Thieme Verlag, Stuttgart, 1977, pp. 44-136. (17) L. D. Hall, J. F. Manville, and N. S. Bhacca, Can. J . Chem., 47 (1969) 1-17.
76
RENB CSUK AND BRIGITTE I. GLANZER
some 30 Hz (compare, Table 11). The value of J (trans) are found to be larger than J (gauche).These couplings depend on the electronegativity of neighboring substituents. Only a few exceptions to the empirical ranges given in Table I1 are known. trans-Vicinal couplings in the pyranose series depend additionally on the nature of the substituents on the carbon atoms to which the coupled nuclei are themselves bound. The coupling constant decreases as the number of oxygen atoms increases. The factors that control gauche, vicinal coupling depend onlo: the presence of a hydroxyl group trans to the C-C bond bearing the coupling nuclei, the presence of an oxygen atom trans to the fluorine atom by way of the coupling pathway, and also on the number of substituted oxygen atoms on the carbon atoms bearing the coupled nuclei. Long-range Coupling, 4J (*H, '9F). The signs" of these coupling constants vary. The signs for 4J (e,e) in the pyranose series are absolutely positive, whereas 4J (e,a) values are negative; 4J (a,a) are again positive.Ia2O These couplings show the same stereospecificity as compared to their correspondingproton-proton couplings and reach their largest magnitude when a planar M (that is, a coplanar W)relationship is adopted.21 Pyranoses and furanoses both show stereoselectivity in their coupling constants. For the latter, there are possible coupling pathways either via the ring-oxygen atom or exclusively via C-C bonds (compare, Table 111).22 sJ ('H,'9F). Although these long-range coupling-constants have been observed for a few compounds, their practical use remains small. An extended "M" arrangement is anticipated to be the favored pathway for
jJ
Ring form Pyranose Furanose
TABLEI1 (W, '9F) Couplings
Orientation
Coupling constant (in Hz)
trans-diaxial
21-30 0-18 14-30 2-1s
gauche trans cis
L. D. Hall, R. N. Johnson, J. Adamson, and A. B. Foster, Can. J . Chem., 49 (1971) 1 18- 123. A. B. Foster, J. H. Westwood, B. Donaldson, and L. D. Hall, Carbohydr. Res., 25 (1972) 228-23 1. A. B. Foster, R. Hems, and L. D. Hall, Can. J . Chem., 48 (1970) 3937-3945. A. B. Foster, R. Hems, L. D. Hall, and J. F. Manville, Chem. Commun., (1968) 158-159. L. D. Hall and P. R. Steiner, Can. J . Chem., 48 (1970) 2439-2443.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
77
TABLE111 41 (IH,
Ring form Pyranose Furanose
19F) Coupling
Constants Coupling constant (in Hz)
Orientation" e, e e, a a, a trans cis
via via via via
oxygenb C-C bonds' oxygenb C-C bonds'
-4-5 -0- 1 -0.5-2.5 5.5-8 -0.7 1.o-2 - 1.7-2.4
-
" The symbol e stands for equatorial, and a for axial. * Corresponds to a coupling of F-1 to H-4. Corresponds to a coupling of F-1 to H-3.
such couplings, and the couplings reach a maximum when the coupled nuclei are trans-coplanar to the bond that is the midpoint of the coupling pathway.23In addition, an oxygen atom in the coupling pathway leads to increased values as compared to an all-carbon pathway.24 6J (IH,19F). There are only a few examples of this long-range coupling; their use in conformational analysis seems to be negligible. 2. 13C-N.m.r. Spectroscopy
a. Chemical Shifts.-I3C-N.m.r. spectroscopy at natural abundance provides insights on structural and conformational behavior in solution, combined with the advantage of less-crowded and more-readily interpreted spectra. An excellent article on 13C-n.m.r. data for monosaccharides has been published in this Series.25In general, fluorine substitution in carbohydrates results in a significant, low-field shifting of the signal of the adjacent carbon a t o ~ n . ~ ~ , ~ ' b. "C-I9F Coupling Constants.-The measurement of these coupling constants, using proton-broad-band decoupling, is facile, and greatly aids in the interpretation and assignment of the spectra. 'J ( I T , 19F).These coupling constants are of negative sign,28and their magnitude depends on several factors: l o (I) The magnitude increases with (23) L.Phillips and V. Wray, J. Chem. Soc., B , (1971)1618-1624. (24) V. Wray, J . Chern. Soc., Perkin Trans. 2 , (1976)1598-1605. (25) K.Bock and C. Pedersen, Adv. Carbohydr. Chem. Biochem., 41 (1983)27-66. (26) P. KovAC and C. P. J. Glaudemans, J . Carbohydr. Chem., 2 (1983)313-327. (27) P. J. Card, J . Org. Chern., 48 (1983)393-395. (28) K. Bock and C. Pedersen, Acra Chem. Scand., Ser. B , 29 (1975)682-686.
78
RENE CSUK AND BRIGITTE I. GLANZER
increase in the electronegativity of the atoms attached to the coupled carbon atom. (2) There is dependence on the orientation of the fluorine atom under consideration, including remote effects. Secondary deoxyfluoroglycopyranoses exhibit such couplings of -225 Hz, glycosyl fluorides of - 180 Hz, and 6-deoxy-6-fluoroglycopyranoses of 165 Hz. 2J ( 13C, 19F).The sign of these couplings28was found, or assumed, to be positive and their magnitude depends to a much smaller extent on the electronegativity of the atoms attached to the coupled fragment than does that of 'J ( I3C, IyF).However, they are much more sensitive to the orientation of these electronegative substituents with respect to the fluorine atom.I0 jJ ( 13C, 19F).This coupling shows the same angular dependences as the corresponding fluorine-proton or proton-proton counterpart,I6 thus permitting the development of Karplus-type relationship^^^ ; the sign was assumed to be positive.24 The magnitude depends on the electronegativity of substituents attached directly, or adjacent, to the coupled carbon atom; increasing electronegativity causes a small decrease, whereas a large decrease is observed on change from a trans to a gauche orientation of the coupled nuclei. A large increase in the coupling constant is found if the orientation of an electronegative substituent attached to the middle carbon atom of the coupling pathway changes from trans to gauche relative to the fluorine atom, even though the relative positions of the coupled nuclei are held constant.24 4J( uC, 'V). Although there are only a few examples of this long-range coupling, dependences on orientation may be detected. Observable values could only be obtained for equatorially disposed fluorine atoms (except for those in glycosyl fluoride^).^^
-
3. 19F-N.m.r. Spectroscopy a. 19F-Chemical Shifts.-Because the 19F-nucleus shows spectroscopic behavior similar to that of the IH-nucleus (compare Table I) I9Fn.m.r. spectroscopy was used, even at the very beginning of n.m.r. spectroscopy of carbohydrates. I9F-N.m.r. spectroscopy offers some important benefits: the nucleus is at isotopic abundance, the gyromagnetic ratio is high, and the relevant spectroscopic parameters may be readily extracted from the spectra. Importantly, this nucleus is a probe that is very sensitive to changes in the steric and electronic environment.2yIn this way, lyF-n.m.r.spectroscopy must be regarded as a part of (29) L. Phillips and V . Wray, J . Chem. SOC., Perkin Trans. 2, (1972) 223-228.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
79
the “structural-reporter-group concept” originally developed for IHn. m. r. spectroscopy of oligosaccharides.30 The main difference between 19F-n.m.r.and ‘H-n.m.r. spectra is exemplified by the tremendously enlarged range of chemical shifts. This range reflects the presence of nonbonding electrons on fluorine, in general giving rise to low energy n-r* transitions, and thus the large paramagnetic contributions to the nuclear shielding tensor will cause nuclear deshielding, whereas the diamagnetic contributions are rather small The extensive investigations of single groups of fluorinated carbohydrates has not only provided fundamental information for establishing the structures of the fluorinated derivatives but has also shown I9F to be a very sensitive probe and, as Inch pointed out,5 as an “amplifier” for showing conformational distortions and mobility. The chemical shifts of fluorine atoms are dependent on their site, and their orientation with respect to the carbohydrate ring.29Because only empirical correlations have been made between chemical shifts and stereochemistry, these rules can only be applied to compounds that are closely related structurally to those which have been utilized to establish these correlations.I6 Shifts of I9F although at least one order of magnitude greater than the corresponding IH-values, are therefore generally only indicative, for example, of the chemical environment of fluorine within the molecule. l6 Primary and secondary fluorides may be clearly differentiated; primary resonate at higher field than secondary fluorides; glycosyl fluorides resonate at still lower field. Tertiary fluorides and secondary geminal difluorides resonate still further to low field. The fluorine shifts of a-aldohexopyranosyl fluorides, having an axially oriented fluorine atom, are at higher field than those of the corresponding, equatorially oriented p counterpart^,^^-^^ which, in turn, were found to display temperature-dependent Chemical shifts and chemical-shift differences between pairs of anomers in the monodeoxymonofluoro-D-hexopyranose series were observed to be strongly dependent on the stereochemistry of electronegative substituents in the molecule. In consequence, no a priori distinction between anomers can be made on the sole basis of their respective fluorine shifts.23 The use of fluorine shifts as a probe for structural and conformational (30) J. F. G . Vliegenthart, L. Dorland, and H. Van Halbeek, Adu. Carbohydr. Chem. Biochem., 41 (1983) 209-374. (31) J. B . Lambert and F. G . Riddel (Eds.), The Muftinuclear Approach to N.m.r. Spectroscopy, Reidel, Dordrecht, 1983. (32) L. D. Hall and J . F. Manville, Chem. Ind. (London), (1965) 991-993. (33) L. D. Hall and J. F. Manville, Can. J . Chem., 45 (1967) 1299-1303. (34) L. D. Hall and J. F. Manville, Can. J . Chem., 47 (1969) 361-377.
80
RENE CSUK AND BRIGITTE I. GLANZER
parameters therefore remains of limited value. Furthermore, data reported in the literature need to be viewed with caution because of strong and non-negligible solvent- and temperature-effects on the chemical shifts .35 b. 19F-19F Coupling.-In contrast to IH-I9F and I3C-I9F couplings, I9F-l9F couplings may only be used with caution for stereochemical assignment. Geminal 2J ( I9F, 19F)couplings ranging from -240 to 300 Hz for sp3-hybridized carbon atoms, and some 30-40 Hz for sp2, have been reported. Analysis of 3J ( 19F, I9F) couplings revealed that the angular dependence is more complex than for the corresponding ‘H-IH or IH-l9F couplings. trans-Vicinal were assumed to be more sensitive than gauchevicinal couplings.36These couplings are absolutely negative, and range36 between 10 and 20 Hz. The values of 4J (I9F, I9F) may be of different sign, with J (e,e) being absolutely negative, and J @ , a )and J (a,a)being positive.I7 Although the magnitude of coupling depends on the relative orientation of substituents, there is no enlarging effect of an “M” relationship of the coupled nuclei.21 The values of 5J (I9F, 19F)are of variable sign and are presumed to occur by way of through-bond interaction; their stereospecific dependences seem to be rather complex.I0 4. Other Nuclei
There is little known in the carbohydrate field about coupling of fluorine with nuclei other than ‘H, I3C, or 19F.Tronchet and coworkers37investigated the 2H-19Fcoupling in (2)-and (E)-3-deoxy-3-C-(fluoromethylene)1,2: 5,6-di-O-isopropylidene-a-~-ribo-hexofuranose deuterated at the sp2hybridized fluoromethylene group. The 2J ( 2H, I9F) coupling is, in comparison with the corresponding IH-I9F coupling, significantly lessened (12.4 Hz us. 82 Hz), thus limiting its use and potential significance.
111. TABLES 1. Guide to Use of the Tables
All fluorine chemical-shifts given in this compilation have been converted to the 6 scale, with trichlorofluoromethane (Freon-I 1) as refer(35) H. Giinther, NMR-Spektroskopie, G. Thieme Verlag, Stuttgart, 1973. (36) L. D. Hall, R. N . Johnson, J. Adamson, and A. B. Foster, Chem. Commun., (1970) 463-464. (37) J. M. J. Tronchet, D. Schwarzenbach, and F. Barbalat-Rey, Carbohydr. Res., 46 (1976) 9-17.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
8I
TABLEIV Conversion Factors Used Throughout this CompilationB Reference material
Shift (to Freon-11) (in p.p.m.)
Reference material
Shift (to Freon-11) (in p.p.m.)
F2 C~HSSO~F CFCI3 CF2CIi C6HsCF3 CFC12-CFCI2 CF$Z02CHX
+422.9 +65.5
CF3C02H CFICCIX CF3COCF3 CFC(OH)2CFj
-78.5 -82.2 -84.6 -92.7 -113.1 - 120.0 - 162.9
0.0
-6.9 -63.9 -67.3 -74.2
FC6H4F-p C6F6
ence, and with positive shifts to high frequency of the reference, using the conversion factors shown in Table IV. Because some authors omit indication of sign or standards, or change conventions, some errors may be present in the tables. Tables V-LVII detail ‘H and I9F shift and coupling information, and Tables LVIII to LXXI incorporate the 13C-n.m.r.data. The data within this compilation are arranged according to the following outline: hexoses prior to pentoses, followed by anhydro sugars, sugar acids and lactones, amino sugars (and their synthetic, N-containing precursors), mono-, di-, and tri-deoxy sugars, branched derivatives, ketoses, polyfluorinated monosaccharides, and, finally, difluorinated amino sugars. Within this compilation, and even within each table, pyranoid derivatives are listed prior to their furanoid counterparts, hexoses prior to pentoses, functionalized prior to deoxy compounds; the arrangement within each “sub-table” is made alphabetically. The tables contain nearly all of the n.m.r. information currently available in the literature. Although there are more fluorinated monosaccharides known, for many of them no n.m.r. data have been reported so far. Throughout the Tables, “S” stands for “solvent”: A for hexadeuterioacetone, B for hexadeuteriobenzene, C for deuteriochloroform, D for deuterium oxide, F for liquid hydrogen fluoride, H for water, M for tetradeuteriomethanol, N for dichlorodideuteriomethane, and s for hexadeuteriodimethyl sulfoxide.
(38) V. Wray, Annu. Rep. NMR Specfrosc., 10B (1980) 5.
RENE CSUK AND BRIGITTE I. GLANZER
82
TABLEV 'H- and I9F-N.m.r. Data for Hexopyranosyl Fluorides
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
Jz,~
53.4
54.5
55.6
55.6
56,6
JF,l
JF,Z
JFJ
JF,4
JFJ
Jv.6
JF.6'
6F
S
References
2,3,4,6-Tetra-0-acetyl-o-allopyranosyl fluoride a anomer 5.55 4.79 3.2 3.2 53.5 26.0 p anomer 5.41 5.07 7.3 2.8 52.7 12.0
5.32 3.0
5.12 10.2
4.00 4.6
5.38 2.8
5.05 9.5
3.96
4.20
- 145.5
17"
4.20
- 146.3
17"
2.3
2,3,4,6-Tetra-0-acetyl-~-gdactopyranosy~ fluoride a anomer 5.82 5.27 5.50 2.8 10.0 b2.3 53.0 21.8 p anomer 5.55 5.09 5.06 7.0 10.3 3.4 52.0 12.6 D-Glucopyranosylfluoride a anomer 5.66 3.0 53.2 27.2 p anomer 5.31 6.66 52.0 12.0 2,3,4,6-tetra-O-acetyla anomer 5.74 4.94 5.48 2.7 10.0 9.5 52.8 23.8 p anomer 5.40 5.12 5.20 6.6 9.0 9.0 52.5 12.0
5.55
1.8
4.34 5.1
5.41 2.0
3.69 b4.9
4.18 7.3
%.0
4.06 10.8 4.15 b11.4
-150.1
17,32 a
-141.9
17,32 u
- 146.2
23
-139.1
23
5.14 9.7
4.18 2.0
4.28 4.2
4.12 12.7
- 149.9
14,15, 17,32,33, 39,40"
5.20 9.4
3.92 3.0
4.30 5.0
4.22 12.8
- 137.8
14,15, 17,32,33, 40"
3.60
- 147.5
14,15, 17
2,3-di-O-acetyl-4,6-O-benzylidenea anomer
5.65 3.0 53.0
4.88 9.8 24.6
5.43 9.4
4.30
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
83
TABLEV (continued) Compound H-1 H-2 51.2
JFJ
JF,Z
H-3
H-4
H-5
H-6
H-6‘
J3.4
J4.5
55.6
55.6’
J6,6’
JFS
JF,~
JFS
JF,~
JF,6‘
&F
S
References
p anomer
5.55 6.2 53.4
5.02 5.34 4.5 7.8 8.8 11.6 3,4,6-tri-O-acetyl-2-O-methyla anomer
3.60
-138.1
2.5
A
14,15, 17
C
41‘
C
41d
24.4
p anomer 6.4
2,3,4,6-tetra-O-benzoyla anomer
6.19 2.8 53.2
5.64 6.23 5.99 9.6 9.6 9.5 23.7 p anomer 5.26 5.75 6.23 5.84 5.7 8.6 8.6 8.6 51.5 10.3 3,4,6-tri-O-benzoyl-2-O-methyla anomer 5.84 3.65 5.95 5.63 2.7 9.6 9.6 9.6 . 52.0 24.3 p anomer 5.48 3.62 5.70 5.61 6.0 7.8 8.5 8.5 52.4 10.4 2,4,6-tri-O-benzoyl-3-O-methyl(Y anomer 5.70 5.22 4.00 5.63 2.7 9.5 9.5 9.5 53.4 24.3 p anomer 5.63 5.45 3.90 5.60 4.5 6.0 7.5 7.5 51.2 7.5
4.80 4.5
4.74 2.6
5.58 12.2
-148.6
A
17,32
3.87 5.0
4.62 3.6
4.40 11.9
-136.4
B
17,32
4.53 ‘4.3
4.64 ‘3.7
4.42 ‘12.6
-149.9
C
17,32
4.25 5.0
4.65 3.6
4.45 12.3
-135.2
4.32
4.55
4.32
-148.8
Y
C
17,32 (I
B
17,32 (I
4.35 5.0
4.62 5.0
4.55 12.0
-131.8
C
17,32 (1
(continued)
TABLEV (continued) Compound H-1 H-2 Jis J2.3 JFJ
J F ~
H-3
H-4
€I-5
H-6
H-6‘
53.4
J4,s
554
Js.6,
J6.6‘
JFJ
JFC
JFS
JF,~
JF,~’
2,3-di-O-benzoy1-4,6-di-O-methyla anomer 4.06 3.70 3.76 5.9 5.19 5.91 10.0 10.2 9.0 2.8 53.5 23.7 p anomer 5.58 5.2-5.9 3.6 6.0 53.0 6.0 2,3,4,6-tetra-O-benzyl-a5.55 2.68 53.2 25.4 2,3,4,6-tetra-O-methyla anomer 5.67 3.20 3.55 3.28 3.60 3.78 2.7 9.6 10.2 10.2 2.7 2.7 53.5 25.0 p anomer 5.11 6.5 53.0 D - M Q I I I I O ~ ~ I Ifluoride OS~I 2,3,4,6-tetra-O-acetyla anomer 5.66 5.26 5.34 4.18 1.3 10.0 10.0 f4.5 r3.6 48.5 1.5 p anomer 5.45 5.25 5.04 5.04 3.82 4.38 1.9 2.2 5.7 4.7 5.7 5.6 51.2 13.9 3,4,6-tri-O-acetyl-2-0-methyl-a2.1
6F
S
References
3.70
C
42
3.9
C
42
-149.0
C
43
-149.9
C
44
-138.7
C
44
-138.2
A
17,32, 40
-142.0
C
28,39, 32
c
41
3.60
f13.0 4.22 11.8
8
0.8
2,3,4,6-tetra-0-benzoyl-a5.84 5.86 5.90 6.22 4.77 4.61 1.1 9.5 e9.5 ‘2.0 ‘4.9 c48.5 ‘1.0 2,3-di-O-benzoy1-4,6-di-O-methyla anomer 5.71 5.69 5.60 3.6 1.6 49.0 1.6
4.49 ‘12.5
4.15
-138.7
C
17,32
C
42
(continued)
85
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES TABLEV (continued)
p anorner 5.75 5.80 5.60 3.7 1.5 3.4 6.9 51.6 12.9 2-O-benzoyl-4,6-di-O-methyl-a5.67 5.47 4.16 3.6 2.0 3.5 8.7 0.5 49.5
3-0-benzoyl-4,6-di-O-methyl-/3-
5.56 1.8 52.8
4.28 3.6 14.6
5.28 6.4
3.5
-
4.1
C
42
-
3.90
C
42
-
3.90
C
42
Ref. 17 reported chemical shifts and coupling constants for solvents A, B, and C. Coupling constant measured in A. J ( F, OMe) = 1.0 Hz.d J (F,OMe) = 1.4 Hz. Coupling constant measured in B. f Coupling constant measured in C. g J (F, OMe) = 0.55 Hz.
(39) C. J. S. Van Rijn, J. D. M. Herscheid, G. W. M. Visser, and A. Hoekstra, Znt. J. Appl. Radiat. Isot., 36 (1985) 111-115. (40)L. D. Hail and J. F. Manville, Chem. Commun., (1968) 37-38. (41) A. B. Foster, R. Hems, J. H. Westwood, and L. D. Hall, Carbohydr. Res., 23 (1972) 316-3 18. (42) c. Pedersen and S. Refn, Acta Chem. Scand., Ser. B, 32 (1978) 687-689. (43) M. Hayashi, S. Hashimoto, and R. Noyori, C h m . Lett., (1984) 1747-1750. (44) G. L. Trainor, J. Carbohydr. Chem., 4 (1985) 545-563.
TABLEVI lH- and '9F-N.m.r. Data for 2-Deoxy-2-Buoro-hexopyranoses and hexopyranosides
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JI,Z
I23
53.4
JW
J5.6
JW
JW
JFJ
JF,Z
IF3
J F ~
JFJ
Jp.6
JFC,
2-Deoxy-2-Buoro-~-g~a~opyranose a anomer 4.44 4.0 10.5 3.5 0.5 50.5 13.3 2.8 /3 anomer 5.06 7.3 7.5 3.2 3.0 51.5 14.5 2.8
SF
S
-203.1
D
References
45,46, 47 a
-202.9
D
45,46, 47 b
(continued)
RENfi CSUK AND BRIGITTE I. GLANZER
86
TABLEVI (continued) Compound H-1 H-2 Ji,z Jzs JF.~
JF,Z
€5-3
H-4
H-5
H-6
H-6'
J3.4
543
55.6
Js,6*
16.6'
JF.~
Jp.4
JFJ
JFC
JF,~'
1,3,4,6-tetra-O-acetyla anomer 6.48 4.90 5.40 5.31 4.32 10.0 3.@ 3.5 4.0 49.0 11.0 3.5 p anomer 5.10 4.41 5.10 5.34 8.0 9.6 3.5 0.0 4.0 51.1 13.1 2.1 2-Deoxy-2-fluoro-~~g~a~opyranoside methyl p4.65 4.38 9.0 9.0 3.0 52.0 methyl 3,4-O-isopropylidene-6-O-trityl-p4.3 4.24 3.41 1.4 1.45 2.0 47.6 trifluoromethyl 3,4,6-tri-O-acetyl-a5.15 4.17 5.32 5.46 4.35 1.o 3.1 10.5 3.5 0.5 48.5 11.0 3.5 2-Deoxy-2-fluoro-~-glucopyranose a anomer 5.39 4.36 3.32 3.66 9.5 0.5 48.9 14.5 p anomer 4.85 4.05 3.32 1.8 8.8 2.5 50.0 14.5 1,3,4,6-tetra-O-acetyla anomer 6.46 4.64 5.56 5.08 4.03 4.0 9.6 9.6 9.6 2.3 0.5 48.5 12.0 p anomer 5.64 4.33 5.23 4.90 3.11 8.1 8.8 9.6 9.1 4.1 3.0 51.0 14.5 2-Deoxy-2-fluoro-n-glucopyranoside methyl 4,6-di-O-acetyl-3-O-benzyl-p4.42 4.39 3.49-4.34 5.05 3.49 1.7 1.7 9.1 9.1 1.7 52.0
4.10
4.00
References
6F
S
-201.1
c
48,49, 50
-208.1
C
45
-203.9
D
51
C
52
4.33
4.03
-211.0
C
45,46, 5334
4.08
-194.8
D
12,23,24, 47,55,56, 57,58,d
4.08
-194.6
D
23,24,47, 55,56,57, 58,'
4.00 12.5
4.22 12.5
-202.9
C
39,48,49, 50,56,51
4.30 1.6
3.98 12.4
-201.4
C
39,56,57, 58,59
-
4.34
C
57
4.03
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
87
TABLEVI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.2
J23
J3.4
34.5
Js.6
55.6'
J6.6'
JFJ
JF,~
JFJ
JFA
JF,S
JF,~
JF,~
methyl 3-0-acetyl-4,6-0-benzylidene-p4.55 4.28 5.45 4.39 3.49 7.6 8.8 9.9 4. I 1.5 49.0 methyl 4,6-0-benzylidene-3-O-methyl-p 4.49 4.25 3.40-3.88 4.38 3.40 7.9 7.9 10.2 4.5 2.7 51.2 methyl 3-0-benzyl-4,6-0-benzylidene-p4.49 4.34 3.75 4.38 3.40 7.8 7.8 8.0 4.6 2.W 51.0 15.0 phenyl 3,4,6-tri-O-acetyl-P5.13 4.57 5.42 5.10 3.85 4.14 7.7 8.6 9.1 9.7 5.2 2.7 3.2 50.0 14.1 trifluoromethyl 3,4,6-tri-O-acetyl-a3.9 0.5
9.7
9.4 11.5
6F
S
References
3.89
C
57
3.88
C
57.60
3.94
C
57,61
4.31 12.0
C
62
-195.4
C
58
-200.8
D
23,24,47, 55,56,58, 63,64,8
-219.3
D
23,24,47, 55,5633, 63,64,*
9.4
2-Deoxy-2-fluoro-o-mannopyra~1ose
a anomer 5.37 4.77 1.95 2.2 7.6 49.1 30.0 p anomer 4.99 4.81 1.0 2.44 20.5 51.3 32.0 1,3,4,6-tetra-O-acetyla anomer 6.09 4.59 5.02 1.9 2.4 10.2 6.3 48.9 27.2 /3 anomer 5.07 5.81 4.87 1.0 2.4 10.0 19.0 51.2 27.0
5.18 9.8
3.88 4.7
4.18 2.2
3.91 12.6
-201.2
C
39,56, 58,63
5.37 10.0
3.81 4.8
4.30 2.3
4.16 12.5
-220.2
C
39,49, 5036, 58,63
3.4
-
4.34
C
63
1,4,6-tri-O-acetyl-3-O-methyl-
a anomer 6.28 4.80 2.0 2.0 7.0 49.0
3.4-4.34 10.0
5.32 10.0
(continued)
RENC CSUK AND BRIGITTE I. GLANZER
88
TABLEVI (continued) Compound H-1 H-2
Jiz
Jw
JFJ
J F ~
H-3
H4
H-5
H-6
H-6’
J3.4
J4.5
15.6
J5,v
J6.6,
JF3
J17.4
JFJ
JF,~
JFC’
p anomer 5.74 4.93 5.26 1.0 2.0 10.0 10.0 19.0 52.0 Methyl 2-deo~2-Buoro-~-maopyraooside 3,4,6-tri-O-acetyI-p4.52 4.82 4.99 5.36 3.54 1.0 2.5 9.9 9.9 17.6 51.0 27.0 4.90 2.0 52.0
S
References
C
63
C
63
C
63
C
63
C
63
5.54 10.0 28.0
C
61
C
61
C
63
4,6,di-O-acetyl-3-O-rnethyl-/3-
4.44 1.0 18.0
&F
3.2-3.7 10.0
5.24 10.0 4.39 4.9
3.38
4.36 6.0
3.24
4.32
4.36
3.2-3.7
3-0-acetyl-4,6-O-benzyIidene-P-
4.57 4.92 5.07 1.0 2.7 10.3 20.0 50.0 25.8 4,6-O-benzylidene-p4.42 4.78 3.24-4.0 1.0 3.0 10.0 20.0 50.0
-
-
4.18
4.0
3-0-benzoyl-4,6-0-benzyIidenea anomer
4.94 3.0 8.0
3.0
4.62 0.0 19.0
5.02 2.5 51.0
5.34 10.0 26.0
4.40 1.0 19.0
4.78 3.0 51.0
3.24
p anomer
3-0-benzyl-4,6-O-benzylidene-p-
-
4.44
Tritluoromethyl3,4,6-~-0~ecetyl-2-deoxy.2-fluoro-~~-mannopyranoeide 1.0 2.5 9.7 9.0 16.0 25.0 ~-Deoxy.~-flnoro-D-t~opyrnnose a anomer
12.2
44.0
-203.4
C
58
D
47
34.2 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
89
TABLEVI (continued)
p anomer 19.7 51.2 32.9 2-Deoxy-2-fluoro-~-tdopyranoride tritluoromethyl3,4,6-tri-O-acetyl-p5.17 4.67 4.99 5.25 4.23 1.0 3.0 3.5 1 .o 16.5 51.0 29.0
-
3.97
-223.5
D
47
-220.0
c
45
Ref. 47 reported a chemical shift of -208.8 a Ref. 47 reported a chemical shift of -208.9 p.p.m. p.p.m. Ref. 48 reported acoupling of 1.2 Hz. Ref. 47 reported a chemical shift of -200.6 p.p.m. Ref. 47 reported a chemical shift of -200.4 p.p.m.fRef. 61 reported a coupling of 4.0 Hz.g Ref. 47 reported a chemical shift of -206.0 p . p m * Ref. 47 reported a chemical shift of -224.5 p.p.m.
(45) J. Adamson and D. M. Marcus, Carbohydr. Res., 22 (1972)257-264.
(46)J. Adamson and D. M. Marcus, Carbohydr. Res., 13 (1970)314-316. (47) M. Diksic and D. Jolly, J . Carbohydr. Chem., 4 (1985)265-271. (48) M. J. Adam, B. D. Pate, J. R. Nesser, and L. D. Hall, Carbohydr. Res., 124 (1983) 215-224. (49) B. I. Glanzer and K. Dax, Eur. Symp. Carbohydr., 3rd, Grenoble, 1985,B.l-24. (50) B. I. Glanzer, Diplomarbeit, Techn. Univ. Graz, 1985. (51) Y. Ittah and C. P. J. Glaudemans, Carbohydr. Res., 95 (1981) 189-194. (52) T. Haradahira, M. Maeda, Y. Yano, and M. Kojima, Chem. Pharm. Bull., 32 (1984) 3317-3319. (53) P. W.Kent, R. A. Dwek, and N. F. Taylor, Tetrahedron, 27 (1971)3887-3891. (54) R.A. Dwek, P. W. Kent, P. T. Kirby, and A. S. Harrison, Tetrahedron Lett., (1970) 2987-2990. (55) G. T. Bida, N. Satyamurthy, and J. R. Barrio, J. Nucl. Med., 25 (1984)1327-1334. (56) G. K. Mulholland and R. E. Ehrenkaufer, J. Org. Chern., 51 (1986) 1482-1489. (57) T. Haradahira, M. Maeda, Y. Kai, H. Omae, and M. Kojima, Chem. Pharm. Bull., 33 (1985)165-172. (58) J. Adamson, A. B. Foster, L. D. Hall, R. N. Johnson, and R. H. Hesse, Carbohydr. Res., 15 (1970)351-359. (59) S. R. Thomas, J. L. Ackerman, J. R. Goebel, M. Davis, J. G. Kereiakes, and Y. Y. Lin, Magn. Reson. Imaging, l(1982) 11-21. (60)S. Levy, E. Livni, D. Elmaleh, and W. Curatolo, J. Chem. Soc., Chem. Commun., (1982)972-973. (61) A. Olesker, A. Dessinges, T. T. Thang, and G. Lukacs, C. R . Acad. Sci. Ser. 2 (Paris), 295 (1982)575-577. (62) J. PacBk, Z.KollnerovB, and M. Cernf, Collect. Czech. Chem. Commun., 44 (1979) 933-941. (63) T.Haradahira, M. Maeda, H. Omae, Y. Yano, and M. Kojima, Chern. Pharm. Bull., 32 (1984)4758-4766. (64)T. Ogawa and Y. Takahashi, J. Carbohydr. Chem., 2 (1983)461-467.
RENI? CSUK AND BRIGITTE I. GLANZER
90
TABLEVII 'H- and '9F-N.m.r. Data for 3-Deoxy-3-fluoro-hexopyr~noses and -hexopyranosides Compound H-1 H-2
H-3
Jw
52.3
J3-4
JF.1
JFZ
JFS
H-4 JF,~
H-5 H-6
H-6'
Js.6
J5,6*
JFJ
J F , ~ JF,~'
References
&F
S
-217.2
A
65
-217.4
C
65
-217.4
A
65
-217.4
A
65,66
-204.3
C
67,68
-200.7
C
67,68
C
69
C
69
D
12,23, 53,70, 71
J6,6'
Methyl 3-deoxy-3-fluoro-~-~opyranoside p anomer 4.48 3.40 4.86 8.0 2.0 2.0 29.0 53.0 4,6-O-isopropylidene-p4.53 3.65 4.97 3.53 8.0 28.0 54.0 27.0 6-O-pivaloyl-p3.42 4.92 3.67 3.86 4.21 4.44 8.0 2.0 6.0 2.0 11.0 30.0 53.0 28.0 6-0-trit yl-/34.62 3.55 4.94 3.80 3.87 3.33 3.50 8.0 1.5 8.0 5.4 2.2 10.0 1.5 53.0 28.0 ~-Deoxy-~-fluoro-~-gPactopyranose 1,2,4,6-tetra-O-acety1a anomer 6.41 5.40 4.86 5.69 4.4 3.95 3.6 10.0 3.6 1.0 4.8 11.4 47.5 6.4 p anomer 5.64 5.38 4.70 5.59 4.24 3.92 8.1 9.5 3.8 0.5 11.5 47.4 5.6 3-Deoxy-3-fluoro-~-gPactopyranos~de methyl 2,4-di-O-benzoyl-6-O-(bromoacetyl)a anomer 5.26 5.54 5.22 5.91 4.25 4.43 4.0 10.0 4.0 1.0 4.0 10.0 48.5 5.5 p anomer 4.60 5.67 4.93 5.87 4.07 4.36 4.36 10.0 4.0 1.0 6.0 6.0 8.0 12.0 47.0 5.0 ~-~eoxy-~-fluoro-~-~ucopyranose a anomer 5.35 3.6 3.9 12.0 53.0 13.6
-195.4
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
91
TABLEVII (continued) ~
Compoond H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.1
JZJ
J3.4
J~J
Js.6
J5.6,
56.6,
JFJ
JF,Z
JFJ
JFA
JFJ
J F , ~ JF.~'
@ anomer 4.75 7.5 0.5 13.0 52.0 6-phosphate a anorner
3.0
12.0
p anomer
52.0
-190.5
3-Deoxy-3-fluoro-~-idopyranose a anomer
3.0
9.0
51.0
46.0
D
12,23, 53,70, 71
D
66
D
66
3.9
-200.4
C
4.09 12.5
-196.2
C
20,53
-194.0
D
53
-194.0
C
53
-198.6
C
20
-197.0
D
53,71
-189.3
D
72
-190.8
D
72
15.0 57.5 15.0 methyl 2-O-acetyl-4,6-O-benzylidene-a4.07 5.39 4.53 3.42 2.99 4.08 3.41 7.5 9.3 9.0 10.0 4.7 9.4 10.6 14.1 53.0 15.1 1.5 2.0 Methyl 3-deoxy-3-8uoro-a-~-gulopyranoside
14.0
References
12.0
benzyl 2,4 ,btri-O-acetyl-P-
p anomer
S
13.0
0.5 13.0 51.0 13.0 1,2,4,6-tetra-O-acetyla anomer 6.31 4.75 4.3 3.2 9.4 9.4 4.0 12.5 52.0 12.5 @ anomer 5.65 5.23 4.60 5.25 3.75 4.29 8.3 8.9 9.2 4.3 2.5 10.0 51.3 12.8 12.8 1.1 1.5 3-Deoxy-3-fluoro-~-~ocopyr~nocl~de benzyl p-
3.0
SF
20
14.0
9.0
3.0 (continued)
RENk CSUK AND BRIGITTE I. GLANZER
92
TABLEVII (continued) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JIJ
J23
J3,4
J4.s
Js,6
Js.6,
J6,6'
JF,I
JF,Z
Jp.3
JF,~
JF,S
JF,~
Jp.6'
~Deoxy-3-fluoro.~-mannopyranose (I anomer 5.23 4.19 4.75 3.62 1.9 3.5 9.4 5.1 7.1 48.6 /3 anomer 4.91 4.19 4.59 3.62 1.1 3.5 9.4 10.0 5.9 2.4 2.1 7.4 48.0 1.2 1,2,4,6-tetra-O-acetyI-a6.14 5.36 4.91 5.46 3.97 4.28 2.0 3.8 9.6 10.1 5.0 2.5 4.7 48.0 11.4 5.8 1.0 0.0
SF
S
References
4.03
D
73
4.03
D
73
4.13 12.5 1.5
C
73
P. J. Card and G. S. Reddy, J . Org. Chem., 48 (1983)4734-4743. D. G.Drueckhammer and C. H. Wong, J . Org. Chem., 50 (1985)5912-5913. J. S.Brimacombe, A. B. Foster, R. Hems, J. H. Westwood, and L. D. Hall, Can. J . Chem., 48 (1970)3946-3952. J. S. Brimacombe, A. B. Foster, R. Hems, and L. D. Hall, Curbohydr. Res., 8 (1968) 249-250. P. KovBe and C. P. J. Glaudemans, J . Curbohydr. Chem., 4 (1985)613-626. N. F. Taylor, B. Hunt, P. W. Kent, and R. A. Dwek, Carbohydr. Res., 22 (1972) 467-469. P. W. Kent, R. A. Dwek, and N. F. Taylor, Biochem. J . , 121 (1971)1OP-llp. A. B. Foster, R. Hems, J. H. Westwood, and J. S. Brimacombe, Curbohydr. Res., 25 (1972)217-227. M . Cernf, J. DoleMovB, J. MBcovB, J. PacBk, T. Trnka, and M. BudeSlnskf, Collect. Czech. Chem. Commun., 48 (1983)2693-2700. TABLEVIII IH- and W-N.m.r. Data for 4-Deoxy-4-fluoro-hexopyranoses and -hexopyranosides
4-DeoKy.Qfluoro-D-gnladopyranose
1,2,3,6-tetra-O-acetyI-p-
8.0 0.8
10.0
2.5 26.5
1.0
-217.4 25.0
1.0
C
19
1.0 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
93
TABLEVIII (continued) ~
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JIJ
JZJ
J3.4
J4.5
55.6
55.6'
J6.6'
JFJ
JF,Z
JFJ
JFI
JFJ
JP,~
J F , ~
Methyl 4-deoxy-4-8uoro-o-gelPctopyranoside 2,3,6-tri-O-acetyl-a5.01 5.20 5.28 4.92 4.06 4.23 3.50 10.5 2.5 2.5 6.5 7.0 3.7 25.5 51.0 29.0 3.7 2,3,6-tri-O-benzoyl-p8.0 0.5
9.8
2.8 25.0
1.2 50.0
4.31 11.5
51.0
49,50 65,74
B
75
C
51
D
76
-219.9
A
65,77
-194.3
D
12,23,78
-195.3
D
12,23
C
12,79
A-M
65,80
27.0 3.86
3.74 12.0
3.81 4.85 3.91 2.50 6.5 29.0 51.0 30.0 ~Deoxy48uoro-o-~uropyraoose a anomer 5.56 3.5 3.5 15.0 49.0 4.5 p anomer 5.01 7.8 0.0 16.0 49.5 4.5 1,2,3,6-tetra-O-acetyI-p-
3.28 6.5
3.34 9.0
8.1
References
C
-219.7
-217.3
3.44
6-0-trityl-a4.41 3.68 3.50"
4.73
S
25.0
6-0-benzoy1-2,3-di-O-benzyl-/327.0 2,3-di-O-benzyl-p4.30 3.69 3.49
SF
3.0
2.0
3.0
2.0
9.5
8.8 10.0 2.5 4.4 12.4 14.5 49.5 2.6 1.6 1.5 Methyl 4-deoxy-4-8uoro-~-~ucopyr~oside a anomer 4.47 3.64 4.0 3.15 3.15 3.5 9.0 9.0 9.0 50.0 3.5 16.5 2,3,6-tri-O-acetyl-a4.65 3.42 3.7 5.70 4.10-4.60 9.5 9.5 3.8
-198.0
B
80
(conrinued)
RENfi CSUK AND BRIGITTE I. GLANZER
94
TABLEVIII (continued) Compound
S
H-1
H-2
H-3
H-4
H-5
H-6
H-6’
J1.z
JZJ
53.4
J4s
Js,6
Js.6,
J6.6’
JFJ
JF,Z
JFS
JF,~
JFJ
Jp.6
J17.6’
4.33
4.67
4.67 12.8
-197.6
C
27
3.89 4.34 4.29 3.21 3.65 4.81 4.7 9.9 2.7 8.4 3.6 9.5 15.8 50.2 4.6 1.9 3.3 0.7 2,3-di-O-rnethyl-a4.76 4.30 3.8 8.8 8.8 3.8 15.0 49.5 Methyl 4-deoxy-4-8uoro-~-tdopyrnnoside Q anomer 4.74 4.77
4.23 12.0 1.3
-196.1
C
12,78
C
78
-217.1
A
65
-215.0
C
65
2,3,6-tri-O-benzoyl-a5.22 5.18 6.12 4.77 3.5 9.0 9.1 10.0 14.7 51.3
6-O-acetyl-2,3-di-O-methyl-a-
6-O-trityl-a4.79
6F
References
b
49.0 4.85 49.0
Ref. 77 reported a coupling of 5.34 Hz. J (F,OMe) = 0.8 Hz.
(74) D. M. Marcus and J. H. Westwood, Curbohydr. Res., 17 (1971) 269-274. (75) A. Maradufu and A. S . Perlin, Curbohydr. Res., 32 (1974) 261-277. (76) T. C. Wong, V. Rutar, J. S. Wang, M. S. Feather, and P. Kov612,J . Org. Chem., 49 (1984) 4358-4363. (77) C. W. Somawardhana and E. G. Brunngraber, Curbohydr. Res., 121 (1983) 51-60. (78) A. B. Foster, R. Hems, and J. H. Westwood, Curbohydr. Res., 15 (1970) 41-49. (79) A. D. Barford, A. B. Foster, J. H. Westwood, and L. D. Hall, Curbohydr. Res., 11 (1%9) 287-288. (80) D. P. Lopes and N. F. Taylor, Curbohydr. Res., 73 (1979) 125-134.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
95
TABLEIX 'H- and WF-N.m.r. Data for bDeoxy-6-fluoro-hexopyranoses and -hexopyranosides Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1J
JZJ
J3.4
J4.5
Js,6
-fs,a.
16.6,
JFJ
JFJ
JFS
Jp.4
JFJ
JF,6
JF.6'
S
References
-229.0 D
81
--229.2 D
81
-230.6 C
81
SF
6-Deoxy-6-Buoro-~-galPctopyranose a! anomer
p anomer
I ,2,3,4-tetra-O-acetyl-a-
15.8
18.5
46.7
46.6
46.6
11.8 48.0 48.0 1,2:3,4-di-O-isopropylidene-a5.55 4.35 4.63 4.27 4.08 4.54 4.58 5.0 2.50 7.90 2.00 6.90 5.2 9.5 1.O 1 .o 13.5 46.2 47.1 Methyl 6-deoxy-6-fluoro-~-gala~opyranoside a! anomer 16.9
46.4
-229.5 C
4431,82
-230.0 D
53,71,81
46.4
2,3,4-tri-O-acetyl-a!6-Deoxy-6-fluoro-~-glucopyranose a anomer 3.51 5.26 3.55 3.75 3.98 3.8 9.8 8.8 9.8 3.6 0.0 28.6 0.7 p anomer 3.53 4.69 3.27 3.50 3.64 7.8 9.2 2.4 26.0 1,2,3,4-tetra-O-acetyIa! anomer 6.33 5.06 5.49 5.13 4.10 3.8 10.2 9.4 10.2 23.1 p anomer 5.74 5.0 5.38 3.84 7.5 9.6 2.3 21.9
-229.0 C
53
4.75 4.66 -231.4 D 1.9 10.8 46.7 48.0
12,23,81,83
4.71 4.70 -230.6 D 3.4 10.6 47.4 47.5
12,23,83
4.44 46.9
4.44 -233.7 C
84
46.9
4.49 4.43 4.2 10.7 47.0 46.8
-233.5 C
84,85,86 (continued)
TABLEIX (continued) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
115
JZJ
J3,4
J4.s
Js,6
Js,6*
166'
JF,~
JF,Z
JFJ
JF,~
J F ~
JFC
JFC.
6-Deoxy-6-tluoro-~-gncopyranoside methyl a anomer
26.2
48.0
48.0
5.0 24.4
4.61 2.0 48.0
4.68 10.0 48.0
/3 anomer
4.23 8.0
2,3,4-tri-O-benzyl-a4.4-4.7 3.55 4.01 9.3
3.55 10.0
3.13
4.4-4.7
References
6F
S
-234.5
C
27,7Ia
-233.1
A
65,1Ib
-234.5
C
44
-233.5
A
65
28.5
41.5
3.86 5.0 24.0
2.0 48.0
48.0
3.83 4.5 21.0
4.52 2.0 48.0
4.68 10.0 48.0
-236.6
A
65
3.74 4.63 5.0 2.0 24.0 48.0 Methyl 6-deoxy-6-~uoro-~-maopyraaoside a anomer
4.70 10.0 48.0
-233.0
A
65
-232.1
A
65
p-nitrophenyl p5.21 8,O phenyl a anomer 5.51 3.58 3.5 10.0
10.0
3.41 9.0
p anomer 5.03 8.0
3.90 10.0
10.0
2,3-O-isopropylidene-a4.87 2,3-di-O-methyl-a4.84 3.63 1.5
3.84
47.5
25.5
49.0
49.0
4.61 2.0 48.0
4.68 10.0 48.0
-235.0
C
65
4.0 3.12
4.66
4.66
-233.6
C
65
22.0
48.0
48.0
a Ref. 77 reported a chemical shift of -219.4 p.p.m. * Ref. 77 reported a chemical shift of -193.5 p.p.m.
(81) L. Evelyn and L. D. Hall,Curbohydr. Res., 47 (1976) 285-297. (82) S. Colonna, A. Re, G. Gelbard, and E. Cesarotti, J . Chem. Soc., Perkin Trans. 1 , (1979) 2248-2252.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
97
A. De Bruyn, M. Anteunis, G. Aerts, and C. K. De Bruyne, Acta Cienc. Ind., 4 (1978) 103-107. E. M. Bessell, A. B. Foster, J. H. Westwood, L. D. Hall, and R. N. Johnson, Carbohydr. Res., 19 (1971) 39-48. M. Sharma and W . Korytnyk, Tetrahedron Lett., (1977) 573-576. M. G. Ambrose and R. W. Binkley, J . Org. Chem., 48 (1983) 674-677.
TABLEX IH- and '9F-N.m.r. Data for Hexofuranosyl Fluorides
D-Gdactofuranosyl fluoride 2,3,5,6-tetra-O-acetyla anomer 5.6 3.3 65.0 19.0 6.5 @ anomer 5.74 5.23 5.08 4.49 0.0 1.4 4.5 4.5 58.0 7.3 1.9 2,3,5,6-tetra-O-benzoyl-P6.04 5.67 5.75 4.96 4.0 5.0 59.0 6.5 1.5 D-GIUCO~IU~OSY~ fluoride 2,3,5,6-tetra-O-acetyla anomer 5.99 5.64 5.56 4.60 3.9 3.0 5.2 8.3 60.8 14.4 1.O p anomer 5.70 5.17 5.47 4.65 0.0 0.0 5.1 9.4 60.3 4.4 5.7 2,3,5,6-tetra-O-benzoyla anomer 6.22 5.54 6.22 5.15 3.7 5.0 6.0 8.6 60.8 16.5 1.O p anomer 5.99 5.64 6.03 5.19 0.0 0.0 5.2 9.0 60.0 4.4 5.2
4.20 12.0
-122.6
C
87
-126.4
C
87
5.42 4.6
4.35 6.8
6.14 4.5
4.7-4.85 7.0
-123.5
C
87
5.28 2.5
4.56 5.5
4.13 12.4
-138.2
C
88
5.33 2.4
4.63 4.6
4.20 12.5
-119.1
C
88
5.84 2.6
4.97 5.1
4.67 12.3
-136.0
C
88
5.88 2.5
5.00 4.6
4.78 12.3
-118.8
C
88
(continued)
98
RENfi CSUK AND BRIGITTE I. GLANZER TABLEX (continued)
D - M P ~ ~ o ~ fluoride o s ~ I 2,3:5,6-di-O-acetoxonium6.12 6.15 6.34 5.96 5.08 5.20-5.50 0.0 6.5 3.0 6.0 8.5 8.0 56.0 5.0 6.0 2,3,5,6-tetra-O-acetyla anomer 5.81 5.43 5.66 4.60 4.15 5.33 4.60 12.5 2.5 5.6 2.0 5.2 4.8 8.5 64.0 14.0 2.0 p anomer 5.80 5.07 5.70 4.47 4.21 5.46 4.62 3.8 5.8 5.1 9.8 12.5 2.6 4.5 65.8 22.4 7.6 2,3:5,6-di-O-benzoxonium5.90 5.4 6.52 6.50 6.77 6.50 0.0 6.5 3.0 6.0 8.5 55.0 5.0 2,3,5,6-tetra-O-benzoyl-a6.05 5.85 6.19 5.12 5.96 5.04 4.70 0.8 5.4 6.0 8.2 2.5 5.1 12.5 59.9 9.0 2.4 2,3:5,6-di-O-isopropylidenea anomer 4.40 4.11 4.06 5.69 4.77 4.85 4.16 0.0 5.9 3.6 6.1 4.5 7.7 8.8 59.5 6.1 p anomer 5.51 4.71 4.84 4.19 4.47 4.09 3.7 6.2 5.4 7.9 5.5 5.5 66.5 15.3 5.4 2,3,5,6-TebP-0-benzoyl-~~-talofuranosyl fluoride 6.00 5.70 4.99 6.00 4.83 4.73 0.0 3.6 6.0 4.0 6.0 12.0 61.0 2.3 4.5 7.5
F
88
-122.8
C
88
-127.3
C
88
F
88
-121.6
C
88
-130.0
C
89,89a
-126.0
C
89,89a
-114.7
C
87
(87) K. Bock, C. Pedersen, and L. Wiebe, Acta Chem. Scand., 27 (1973) 3586-3590. (88) K. Bock and C. Pedersen, Acta Chem. Scand., 26 (1972) 2360-2366. (89) G. H. Posner and S . R. Haines, Tetrahedron Left., (1985) 5-8. (89a) R. Csuk and A. Vasella, unpublished results.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
99
TABLEXI 'H- and "F-N.m.r. Data for 2-Deoxy-2-fluoro- and 3-Deo~y-3-fluoro-hexofuranoses Compound H-1 H-2 Jls J2.3
H-3
H-4
H-5
H-6
H-6'
J3.4
54.5
35,6
55.6'
J6.6'
JFJ
JFS
JF,~
JF.5
JF,6
JF.6,
JF,Z
6F
S
References
l-O-Acetyl-3-O-benzyI-2-deoxy-2-8uoro-5,6-O-isopropy~dene-~~-~uco~anose 6.33 5.10 4.28 4.35-4.43 3.97 4.09 -202.8 C 49,50 3.8 2.6 4.5 5.1 5.8 8.6 6.6 51.0 13.0 3-Deoxy-3-fluoro-1,2:5,6~di-0-i90propropy~dene-~~-g~a~ofuranose 4.06- 3.80 -187.9 C 67 5.90 4.72 4.82 4.08 4.34 6.4 8.0 3.9 0.5 3.3 6.9 6.2 15.0 51.6 23.7 3-Deoxy-3-fluoro-D-g~ucofurPnose 1,2-O-isopropylidene-a-, 5,dcarbonate .. 4.50 4.50 -207.1 C 20 4.96 6.00 4.72 5.08 4.41 7.5 6.6 3.9 0.7 2.5 5.1 10.8 49.9 29.2 1,2:5,6-di-O-isopropylidene-a4.03 4.12 -208.0 C 20,44, 4.29 5.95 4.70 5.01 4.11 6.1 8.8 5033, 4.8 3.7 0.8 2.2 8.3 66,82,90 10.5 49.0 28.0 1,2-O-isopropylidene-a- 3.60 -209.4 C 20 4.00 5.08 4.11 5.92 4.66 8.0 2.0 3.3 0.5 50.0 28.8 10.5 5,6-phenylboronate-a4.40 -207.8 C 20 4.00 5.84 4.67 5.07 4.21 0.5 2.0 7.2 3.6 10.5 50.0 28.9 3-Deoxy-3-fluoro-~-idofuranose a anomer -199.9 D 72 ~~
(I
20.0
p anomer
28.0b a
52.0
20.0 -197.0
50.0
D
14.0b
J (H-I, H-3) = 0.7 Hz. Assignments may have to be reversed.
(90) T. J. Tewson and M. J. Welch, J. Org. Chem., 43 (1978) 1090-1092.
72
RENB CSUK AND BRIGITTE
100
I. GLANZER
TABLEXI1 'H- and I9F-N.m.r. Data for 5-Deoxy-5-fluoro- and 6-Deoxy-6-fluoro-hexofuranosesand -hexofurnnosides Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.2
Jz.3
53.4
54.1
55.6
J5.6
56.6'
JFJ
JF,Z
JFJ
JF,~
JF,S
JF,~
JF,~,
SF
~-~eoxy-5-fluoro-1,2-O-~sopropylidene-~~-glucof~anose 5.84 4.47 4.17 4.17 4.74 3.86 3.65 3.5 2.8 7.9 2.4 5.6 13.1 1.6 47.0 30.0 30.0 5-Deoxy-5-fluoro-1,2-O-isopropylidene-~-~-idof~anose 5.92 4.48 4.20 4.27 4.70 3.82 3.77 3.5 7.9 3.6 4.6 12.6 3.8 3.5 14.0 50.0 23.2 19.0 6-Deoxy-6-fluoro-~-glucofuranose 1,2-O-isopropylidene-a5.95 4.54 4.37 4.10 4.18 4.57 4.67 -233.6 2.5 8.0 5.0 3.0 10.0 4.0 25.0 48.0 48.0 1,2-O-isopropylidene-5-O-benzyl-a-234.0 I ,2:3,5-di-O-methylidene-a-226.6
22.2
47.5
48.0
References
C-D
91
C-D
91
A-C
65
92 C
81.93
-213.7
C
81
-229.2
c
81
32.8 48.1 48.1 3,5-O-benzylidene1,2-O-isopropylidene-a36.5 I ,2:3,5-di-O-isopropylidene-ar-
S
47.5
48.0
(91) R.Albert, K.Dax,S . Seidl,H.Sterk,and A. E. Stiitz,J . Carbohydr. Chem., 4(1985) 5 13-520. (92) L. D. Hall and P. R. Steiner,Can. J . Chem., 48 (1970)451-458. (93) H.C. Srivastava and V. K. Srivastava,Carbohydr. Res, 60 (1978)210-218.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
TABLEXI11 'H- and 1 9 F - N . m . r . Data for Pentopyranosyl Fluorides Compound
H-1
H-2
H-3
H-4
H-5
H-5'
J1.2
J2.3
J3,4
J43
54,s'
Js,sf
JFJ
JFJ
JFJ
JFC
JF,~
JF,s,
D-Arabinopyranosylfluoride 3,4-0-acetoxonium-2-O-methyl(Y anomer 4.5-4.6 5.86 5.9-6.0 3.2 55.0 p anomer 5.94 5.9-6.0 4.5-4.6 3.5 52.0 2,3,4-tri-Oacetyl(Y anomer 3.75 4.11 5.35 5.28.0 11.4 2.5 5.3 49.2 5.3 p anomer 3.69 3.49 5.70 5.30 5.30 5.40 1.9 13.1 2.7 10.4 2.0 54.0 25.0 3,4-di-O-acetyl-2-O-methyl-/35.79 3.69 5.26 5.38 4.10 3.83 2.6 10.4 3.5 1.2 1.8 12.8 0.0 51.5 24.3 3,4-0-benzoxonium-2-O-methyla anomer 5.90 6.1-6.25 4.65-4.8 3.0 52.0 p anomer 6.02 6.1-6.25 4.65-4.8 3.5 52.5 2,3,4-tri-O-benzoyl-a5.53 5.79 5.90 5.71 3.86 4.30 3.0 4.5 3.0 4.5 8.3 11.6 49.5 4.3 3,4-di-O-benzoyl-2-0-methyla anomer 4.01 4.37 5.69 5.57 5.55 3.77 7.9 11.3 2.8 5.1 3.5 4.3 49.5 5.7 0.0 ~
6F
S
References
F
94
F
94
-138.4
C
95
-152.8
B
14,95 (I
C
94 b
-137.7
F
94
F
94
B
32,95
C-A
94
(continued)
101
RENE CSUK AND BRIGITTE I. GLANZER
I02
TABLEXI11 (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-5'
J1.2
J2.3
J3,4
J4.5
J4.r
Js,s
JF,~
JF,I
JF,~
J17.4
JFJ
JFJ'
p anomer 6.02 4.10 5.62 5.76 4.34 3.5 2.6 10.2 1.5 2.0 53.0 24.0 0.0 3(or 4)-O-benzoyl-2-O-methyl-p5.66 3.50 4.00 4.30 4.80 3.5 10.0 3.5 2.0 2.0 53.0 25.0 D-Lyxopyranosyl fluoride 2,3,4-tri-O-acetyl-a5.46 5.34.02 5.0 9.5 2.0 49.1 2.0 2,3,4-tri-O-benzoyl-a5.78 5.84.35 1.8 5.3 9.5 48.6 2.0 D-Ribopyranosyl fluoride 2,3,4-tri-O-acetyla! anomer ~
52.1
6F
S
References
4.09 13.2
C-A
94
4.80
C-B
94
3.73 11.0
4.04 10.0
-141.1
95
- 140.7
32,95 n
- 147.7
C
32,95
- 140.4
A
14,15, 32,95
26.3
p anomer
5.60 5.15 5.30 2.6 3.8 2.0 49.5 d5.0 2,3,4-tri-O-benzoyla anomer 5.88 5.35 6.21 3.5 3.1 2.9 53.5 25.3 p anomer 6.05 5.8 5.86 2.0 1.6 4.2 48.0 3.0 D-XylOpymnOSyl fluoride 2,3,4-tri-O-acetyla! anomer 5.67 4.89 5.49 2.8 10.0 10.0 53.5 23.7
5.20 2.0
4.21 3.0
3.92 13.0
(I
5.48 5.5
5.80 2.3
4.05 10.6
4.42 10.9
- 148.1
C
32,95 96
4.56 2.3
4.31 13.4
-139.9
A
32,95 96 a
5.04 6.0
3.97 10.6
3.75 10.6
- 152.1
C
14,15, 95 (1
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
103
TABLEXI11 (continued) Compound H-1 H-2
SF
S
References
4.24 12.5
-136.6
A
95,97
4.58 10.8
4.08 10.8
-151.6
C
32,95
4.20 3.5
4.60 13.1
-137.3
C
32,95
H-3
H-4
H-5
H-5’
J1.2
52.3
53.4
54,s
54.5‘
Js,s
JFJ
JF,Z
JFJ
JF.~
JFS
JFS’
4.90 3.1
3.73 4.3
5.50 6.0 5.30 2.5
p anomer 5.46 4.90 5.06 5.7 3.5 5.7 52.1 7.9 2,3,4-tri-O-benzoyla anomer 5.95 5.37 6.18 10.1 2.8 10.2 53.1 23.5 p anomer 5.75 5.30 5.66 2.5 3.5 3.5 49.0 6.0
3,4-di-0-benzoyl-2-0-methyla anomer
5.83 2.8 52.2
3.62 9.8 24.5 p anomer 5.59 3.57 3.0 5.1 9.0 51.3
0
5.95 9.8
5.36 6.0 1.o
4.19 11.0
3.96 11.3
C
94
5.60 5.3
5.28 3.1
4.47 4.2
3.92 12.8
C
94
Values given for other solvents, too. J (H-I, H-5) = 0.5 Hz. J (H-3, H-5a) = 1.3 Hz; J (H-3, H-5e) = 0.9 Hz.* Refs. 14 and 15 reportedJ (H-2, F-I) = 7. I Hz in C, whereas Refs. 32 and 95 reported 3 Hz. J (H-3, H-5’) = 0.7 Hz. L.
(94) S. Jacobsen, S. R. Jensen, and C. Pedersen, Acta Chem. Scand., 26 (1972) 15611568. (95) L. D. Hall and J. F. Manville, Can. J . Chem., 47 (1969) 19-30. (96) B. Coxon, Tetrahedron, 22 (1966) 2281-2302. (97) L. D. Hall and J. F. Manville, Carbohydr. Res., 4 (1967) 512-513.
RENfi CSUK AND BRIGITTE I. GLANZER
104
TABLEXIV *Hand '9F-N.m.r. Data for 2-Deoxy-2-fluoropento-pyranoses and pyranosides ~~~
Compound H-1 H-2
H-3
H-4
H-5
H-5'
J1.2
JZJ
J3,4
545
54,s'
Js,r
JPJ
Jr.2
JFJ
Jr.4
Jr.5
JPJ'
6F
1,3,4-Tri-0-acetyl-2-deoxy-2-fluoro-~~-arab~nopyranose
6.44 4.0
4.92 5.38-5.46 3.82 4.05 -207.7 10.0 14.0 48.0 10.8 3.5 1.5 Trifluoromethyl3,4-di-O-acetyl-P-~-arnbinopyranoside 5.80 4.90 5.23-5.53 4.13 3.82 -208.0 3.5 9.0 1.5 1.5 13.5 "6.0 46.0 8.0 1.5
1,3,4-Tri-0-acetyl-2-deoxy-2-fluoro-~~-1y~opyranose 5.90 2.4 12.0
4.83 2.4 48.0
5.18
7.2 17.6
4.98-5.09 4.0
4.10 6.0
3.49 12.8
-201.0
S
References
C
48,49, 50
C
53,98
C
4930
C
539
Trifluoromethyl3,4-di-O-acetyl-~-~-lyxopyranoside 3.8 3.8 3.8 3.0 44.2 8.5 2-Deoxy-2-fluoro-~-ribopyranose
2.8
13.1
-214.0
b
%P-
2.3
4.1
7.4
1,3,4-tri-O-acetyla anomer 6.06 4.12 5.48 2.1 2.1 3.5 11.7 8.4 46.9 p anomer 6.23 4.56 5.40 3.2 3.2 6.5 48.0 25.2 5.21 3.0 50.0
6.0 3.0 28.0
100
5.10 3.5
3.13 6.9
4.06 12.1
-202.9
C
49,50, 101
5.19 3.2
4.03 4.8
3.93 12.9
-202.4
C
101
4.26 3.0
4.58 13.0
A
102
C
49SO
1,3,4-Tri-O-benzoyl-P-~-ribose 6.66 3.0 6.5
D
5.75 2.0
2-Deoxy-2-fluoro-~-xylopyranose
I ,3,4-tri-O-acetyl-a4.58 4.94d 6.30 4.3 9.8 5.5 48.0 10.3
5.49d 6.3
4.01
11.5
3.80
11.1
-195.9
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
I05
TABLEXIV (continued) Compound H-1 H-2
H-3
H-4
H-5
H-5‘
JI,Z
12.3
53.4
54,s
J4,5*
J5.5’
JFJ
JF,Z
Jp.3
JF,~
JF,~
JFJ’
SF
S
References
-214.0
C
53,99
Trifluoromethyl 3,4-di-0-acetyl-cu-~-xylopyranoside 3.8 0.5
9.8 48.0
9.5 1.0
9.5
6.5
10.0
Ref. 98 reported a coupling of 0.0 Hz. Ref. 53 reported J (F, H-1) = 6 and J (F, H-3) = 0.0 Hz. Values also given for other solvents. ,IThe assignments may have to be reversed.
(98) (99) (100) (101)
E. L. Albano, R. L. Tolman, and R. K. Robins, Carbohydr. Res., 19 (1971) 63-70. C. G. Butchard and P. W. Kent, Tetrahedron, 27 (1971) 3457-3463. W. K. Olson, J. Am. Chem. Soc., 104 (1982) 278-286. J. T. Welch and S. Eswarakrishnan, J . Chem. Soc., Chem. Commun., (1985)
186- 188. (102) R. J . Cushley, J . F. Codington, and J. J. Fox, Carbohydr. Res., 5 (1967) 31-35.
TABLEXV IH- and 19F-N.m.r.Data for 3-Deoxy-3-fluoro- and 4-Deoxy-4-fluoro-pentopyranosesand -pentopyranosides Compound H-1 H-2
H-3
H-4
H-5
H-5’
51.2
JZJ
J3.4
54,s
J4.5
J5.s
JFJ
JFJ
JF,~
JF,~
JF,S
JFJ’
6F
S
-202.0
H
53
-200.0
H
53
References
3-Deoxy-3-Buoroxylopyraoose b
13.6 57.0 1,2,4-tri-O-acetyl-~a anomer 6.26 4.0 4.0 p anomer 5.71 5.14 4.57 6.5 7.9 7.9 12.4 49.4
12.6
5.07 8.0 12.4
3.48 5.0
4.18 12.2 4.2
-195.3
C
11
C
11,20
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
106
TABLEXV (continued) Compound H-1 H-2
H-3
H-4
H-5
H-5’
JI,Z
J2,3
53.4
J4,5
J4.s
J5.5’
JFJ
JF,~
JF,~
JF,~
JFJ
JF,Y
Benzyl 3-deoxy-3-fluoro-P-~-xylopyranoside 4.39 3.49 4.23 3.78 3.91 3.25 7.6 8.4 8.4 5.6 10.1 11.3 13.4 52.4 13.5 5.7 1.0 Methyl 4-deoxy-4-fluoro-~-arabinopyranoside a! anomer 4.68 4.74 3.5 50.0 p anomer 4.18 3.66 3.68 4.74 3.61 4.10 7.0 2.0 1.0 3.0 13.0 1.5 31.0 49.0 33.0 26.0
S
SF
References
A
103
-201.5
C
65
-205.9
C
65
For the furanoid counterpart, a chemical shift of - 197.5 was reported. For the furanoid counterpart, a chemical shift of - 194.0 p.p.m. was reported; J (F, H-2) = 13 Hz, J (F, H-3)= 55 Hz, and J (F, H-4)= 13 Hz.
(103) A. De Bruyn, M. J. Anteunis, G. Aerts, and E. Saman, Curbohydr. Res., 41 (1975) 290-294.
TABLEXVI ‘H- and I9F-N.m.r. Data for Pentofuranosyl Fluorides
D-Arabinofuranosyl fluoride 2,3,5-tri-O-benzoyl-a!6.17 5.74 5.75 4.95 4.88 0.9 0.5 4.4 3.3 5.8 58.4 6.4 0.7 1.5 3 ,5-di-O-benzoyl-2-O-methylQ anorner 5.91 4.22 5.45 4.81 4.59 0.5 0.8 3.2 5.4 3.8 59.2 6.8 0.5 1.5 p anomer 5.56 3.86 5.69 4.27 4.54 3.5 6.6 5.4 5.6 3.8 63.8 20.3 6.0
A
104
4.65 11.5
A
94
4.75 11.5
C-B
94
4.73 12.1
-123.8
(continued)
107
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
TABLEXVI (continued) Compound H-1 H-2
H-3
H-4
H-5
J1.2
Jz.3
J3.4
54,s
54,s
H-5' Jw
JF,I
JF.2
JFJ
JF,~
JF.5
JF,s*
S
References
C
105.106
c
105
F
107
-122.0
c
107
-128.7
C
107
F
107
SF
2,3,5-tri-O-benzyla anomer 5.78 63.0
9.0
p anomer
5.65
-121.0
66.0 3.0 D-Lyxofuranosyl fluoride 2,3-acetoxonium-5-O-acetyl-a6.27 6.1-6.6 5.0 4.5-4.8 0.0
b
55.0
2,3,5-tri-O-acetyla anomer 63.0
67.0
10.0
p anomer 22.5
0.0
6.5
2,3-benzoxonium-5-O-benzoyl-a6.58 6.3-6.8 0.0 55.0 2,3,5-tri-O-benzoyla anomer 6.03 5.83 6.09 0.8 5.4 6.0 8.5 61.0 p anomer 5.48 6.21 6.10 3.5 5.8 5.8 67.0 21.5 D-Ribofuranosyl fluoride 2,3,5-tri-O-acetyla anomer 67.7
5.6
5.1-5.3
d
c
107
-133.8
C
107
-133.1
c
107
5.06 6.0 2.2
4.6-4.8 6.0
-121.0
5.00 6.0 6.0
4.6-4.8 6.0
r
20.7
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
108
TABLEXVI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-5’
Ji.2
52.3
J3,4
J4,s
J4.5’
Jss,
JFJ
JFJ
JFJ
JF,~
JF,S
JFJ
6F
S
References
p anomer 61.8
4.2
2.3
-116.6
C
107
4.51 11.9
-115.8
A
104
4.42 12.4
-115.5
A
104
6.9
2-0-acetyl-3,5-di-O-benzoyl-p-
5.80 0.5 60.9
5.55
4.7 4.7
5.74 6.9 2.4
4.79 3.5 6.7
4.68 4.6
3-O-acetyl-2,5-di-O-benzoyl-p5.95 0.5 61.6
5.70 5.0 4.5
5.62 5.0 1.7
4.74 4.5 7.9
4.68 5.4
6.04 5.81 5.75 0.5 4.9 4.9 61.3 4.9 2.1 2,3,5-tri-O-benzoyla anomer 6.30 5.51 5.86 3.2 6.9 2.3 64.4 20.6 0.0 p anomer 6.18 5.96 6.02 0.5 4.8 5.8 61.5 4.8 2.2 2,3,5-tri-O-benzyla anomer 5.64 3. I 66.0 24.0 p anomer 5.63
4.82 3.6 7.2
4.61 5.3
4.25 12.1
-115.7
4.93 3.1 1.0
4.76 3.5
4.61 12.1
-133.3
5.11
4.89 5.2
4.69 12.2
-115.9
0
5-O-acetyl-2,3-di-O-benzoyl-p-
63.5 D-Xylofuranosyl fluoride 2,3,5-tri-O-acetyla anorner 5.95 5.13 5.56 3.6 6.5 6.5 61.8 17.2 p anorner 5.63 5.18 5.34 1.0 0.5 5.5 60.5 5.2 0.5
3.9 6.6
A
104 a
A
104 (1
A
104 a
-133.0
C
106
-116.0
C
106
4.74 4.8 1.4
4.31 4.1
4.13 12.4
-134.8
C
107
4.70 5.3 5.2
4.29 7.1
4.20 11.4
-113.2
C
104
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
109
TABLEXVI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-5’
JIJ
J2.3
J3,4
54.5
JW
JS,Y
JF.1
JF,2
J F ~
JF,~
JFJ
JF,s~
2,3,5-tri-O-benzoyl-p-
S
SF
References
C
107
F
94
4.48
C
94
5.69 4.96 4.70 4.70 5.2 5.5 6.5 62.6 5.9 6.0 3,5-benzoxoniurn-2-O-rnethyl-~6.09 4.85 5.97 5.97 5.4 0.0 0.5 4.2 60.0 4.0
C
94
F
94
5.96
5.67
5.09 4.5-4.8 6.0 6.0 61.5 4.5 6.0 3,5-acetoxoniurn-2-O-rnethyl-/36.03 4.6 5.72 5.72 5.2 0.0 4.0 61.0 3.5 3,5-di-O-benzoyl-2-O-rnethyla anorner
5.91 3.6
62.5
4.22
6.2 18.0
5.95 5.8
5.78 6.7
p anomer
5.84
4.98 5.9 1 .o
4.48 5.9
-118.5
4.13 1.0
a Also reported for a solution in C. Ref. 106 reported the data for the L enantiorner. J (F-1, Me-C+) = 2.90 Hz. d J (F-1, Me-C’) = 2.90 Hz. e.J (H-I, H-3)= 0.6 Hz.
(104) L. D. Hall, P. R. Steiner, and C. Pedersen, Can. J . Chem., 48 (1970)1155-1165. (105) W. Rosenbrook, Jr., D. A. Riley, and P. A. Lartey, Tetrahedron Lett., (1985)3-4. (106)T.Mukaiyama, Y. Hashimoto, and S. I. Shoda, Chem. Lett., (1983)935-938. (107) K.Bock and C. Pedersen, Acta Chem. Scand., Ser. B , 30 (1976)727-732. TABLEXVII
IH-and 19F-N.m.r. Data for 2-Deoxy-2-fluoropento-furanoses and -furanosides Compound H-1 H-2
H-3
H-4
H-5
H-5’
JI,~
52.3
J3.4
54,s
J4,v
Js.5
JFJ
JF.~
JFJ
JF,~
JFJ
JFJ,
2-Deoxy-2-fluoro-~-arabinofuranose Sphosphate, sodium salt a anorner 5.30 4.90 0.0 0.0 9.5 68.0
SF
S
D
References
66 (1
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
I10
TABLEXVII (continued) Compound H-1 H-2
H.3
H-4
H-5
H-5'
51.2
52.3
53.4
54.5
54,s
JW
JFJ
JF,~
JF,~
JF,~
JF,S
JF,~
p anomer
5.20 4.0 12.0
66 (1
68.0
1,3-di-O-acetyl-5-0-benzoyl-a5.0 5.24 4.51 48.0 5.10 49.0
C
108
A
109
C
108
N
110
C
109
C
108
C
I08
22.0
1,3-di-O-acetyl-5-0-benzyl6.26 0.7 10.5
References
S
D
4.80
6.33
10.0
6F
5.25 4.5 22.8
4.47 4.5
3.74
3.74
1-0-acetyl-5-O-benzoyI-3-O-formyl-a-
6.45 5.12 5.45 4-. 0.0 9.5 50.0 22.0 1,3,5-tri-O-benzoyl-a6.7 5.4 5.61 4.749.0
1,3-di-O-benzoyl-5-0-benzyl6.75
5.50
9.0 49.0 5-O-benzo yl-
5.60 3.4 19.5
4.67 5.0
3.86
3.86
a anomer
5.3 0.0 9.5
4.98 0.0 68.0 p anomer 5.28 4.89 3.5 12.0 68.0 1,3,5-tri-O-benzyl-a5.25 5.03 4.36 1.0 2.4 7.3 12.8 51.2 5-0-benzyl5.42 4.87 4.23 3.86 1.6 6.0 9.7 50.0
3.86
3.63
C
111
3.56
3.56
C
109
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
III
TABLEXVII (continued) Compound
H-1
H-2
H-3
H-4
H-5 H-5’
Ji.2
J2.3
J3,4
54.5
54,s.
Js,sf
JFJ
JF,Z
JF3
JF,~
JFS
JF,S
SF
Methyl 2-deoxy-2-fluoro-a-~-arabinofuranoside 4.96 4.85 3.70 4.5 1.0 2.6 12.0 52.0 3.5-di-0-benzyl5.09 1.o 12.0
S
References
A
109
C
112
5-0-benzyl5.06 4.82 4.10 3.64 3.64 C 109 I .6 5.5 10.3 51.0 1-0-Acetyl-2-deoxy-2-fluoro-5-0-(methoxymethyl)-a-D-nbofuranose 6.40 5.07 4.29 4.52 3.69 3.72 -216.8 C 49,50 10.1 4.4 5.6 2.4 51.3 4.4 Methyl 3-O-benzoyl-5-O-benzyl-2-deoxy.2-fluoro-&noside 5.08 5.00 5.64 4.71 3.71 3.71 C 1 I3 1.6 5.5 5.5 13.4 49.5 16.5 J (C-S, P) = 8 Hz.
(108) U. Reichrnan, K. A. Watanabe, and J. J. Fox, Carbohydr. Res., 42 (1975) 233-240. (109) J. A. Wright, N. F. Taylor, and J. J. Fox, J . Org. Chem., 34 (1969) 2632-2636. (I 10) C. H. Tann, P. R. Brodfuehrer, S. P. Brundidge, C. Sapino, Jr., and H. G. Howell, J . Org. Chern., 50 (1985) 3644-3647. (111) T. L. Su, R. S. Klein, and J. J. Fox, J. Org. Chem., 47 (1982) 1506-1509. (112) T. L. Su, R. S. Klein, and J. J. Fox, J . Org. Chem., 46 (1981) 1790-1792. (113) J. A. Wright and J. J. Fox, Carbohydr. Res., 13 (1970) 297-300.
RENfi CSUK AND BRIGITTE I. GLANZER
I12
TABLE XVIII 'H- and 19F-N.m.r. Data for 3-Deoxy-3-fluoro-D-pento-furanosesand -furanosides Compound H-1 H-2
H-3
H-4
H-5
H-5'
JIJ
J2.3
53.4
J4.5
54,s
J5.5'
JFJ
JF,~
JFJ
JF.~
JFJ
JF.~'
SF
S
Methyl 2,5-di-O-benzoyl-3-deoxy-3-fluoro-~~-arabinofuranoside -188.0 C
References
53,71
7.0" 46.0 10.0" 3-Deoxy.3-fluoro-1,2-O-isopropyl~dene-5-O-~tolyls~onyl-~-~-~lofuranose 5.86 4.64 4.90 4.70 4.10 -210.6 C 20 3.8 0.5 2.0 7.0 10.5 50.5 25.0 Methyl 2,5-di-O-benzoyl-3-deoxy.3-fluoro-/3-~-xylofuranoside -203.0 C 53,7 1 15.0 56.0 24.0 3-Deoxy-3-fluoro-1,2-O-isopropylidene-~-~-~y~~-pentodi~do-l,4-furanose 6.16 4.76 5.25 4.62 9.67 -205.5 C 114 3.7 0.5 2.6 1.2 10.0 50.0 31.5 The assignments may have to be reversed.
(114) J. M. J. Tronchet, B. Gentile, A. P. Bonenfant, and 0. R. Martin, Helv. Chim. Acfa, 62 (1979) 696-699.
TABLE XIX 'H- and lgF-N.m.r. Data for 5-Deoxy-5-fluoro-~-pento-furanoses and -furanosides Compound H-1 H-2
H-3
H-4
H-5
H-5'
JI,~
52.3
J3.4
54.5
54,s
J5.5,
JF,I
JFJ
J F ~
JF.~
JFJ
JFJ-
6F
S
References
-227.3
D
81
-232.5
C
81
-232.1
C
81
5-Deoxy-5-fluoro-~-ribofuranose 23.5 50.0 Methyl 5-deoxy-5-fluoro-~-ribofuranoside 2,3-di-O-acetyl29.5
47.5
50.0
47.5
2,3-O-isopropylidene(Y anorner 30.0
47.5
47.5 (continued)
I 13
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLEXIX (continued) Compound H-2 H-1
SF
S
References
-224.8
C
81
10.5 47.5 47.5 3-0-Benzyl-5-deoxy.5-fluoro-1,2-O-isopropyl~dene-~-~-xy~ofuranose 5.94 4.60 3.97 1.45 4.64 4.58 C 3.4 0.7 3.0 9.0 16.0 42.0 42.0
115
H-3
H-4
H-5
H-5'
Ji,z
52.3
53.4
54.5
J4.5
Js,5*
JF.I
JFJ
JFJ
JF.~
JF.~
JF.~'
p anorner
(115) P. W. Kent and R. C. Young, Tetrahedron, 27 (1971) 4057-4064.
TABLEXX 'H- and I9F-N.m.r. Data for Fluorinated 1,5-Anhydrohexopyranose Derivatives Compound H-2 H-1
H-3
H-4
H-5
H-6
H-6'
JI,Z
JZ,3
53.4
54,5
55.6
Js,~
56.6'
JFJ
JF,Z
JF,~
JF,~
JF,~
JF.6
JF,~
SF
S
References
3,4,6-Tri-0-acetyl-1,5-anhydro-2-deox~2-fluoro-l-C-methyl-~-~-glucopyranose 4.32 4.53 5.23 4.76 3.80 4.19 3.92 C 39 0 5.9 8.8 8.8 9.4 5.0 2.5 12.1 1.5 49.5 12.6 1,5-Anhydro-6-deoxy-6-fluoro-~-ara6~~~-hex-l-enitol 3,4-di-O-acetyl- 1,2-dideoxy6.61 4.90 5.0-5.48 4.15-4.75 5.0-5.48 A 116 b 6.6 3.2 47.0 3,4-di-O-benzyl117 6.39 4.4-5.1 4.1-4.35 3.7-4.1 4.1-4.35 4.4-5.1 -235.4 C 4-0-benzyl-3-deoxy6.29 4.5-4.8 2.27
24.6
47.2
3.47-4.50 29.4
47.2 4.67
48.0
-235.8
C
1 I7
48.0
" M e : 8 = 1 . 3 6 , J ( F , M e ) = 2 . 6 , a n d J ( H - l , M e )=6.9Hz. b J ( H - I , H - 3 ) = 1.2Hz.
(116) M. Sharma and W. Korytnyk, Carbohydr. Res., 83 (1980) 163-169. (117) I. D. Blackburne, P. M. Fredericks, and R. D. Guthrie, Aust. J . Chem., 29 (1976) 381-391.
RENE CSUK AND BRIGITTE I. GLANZER
1 I4
TABLEXXI
'H-and 19F-N.m.r.Data for Fluorinated 1,6-AnhydrohexopyranoseDerivatives Compound
H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JI,Z
Jz.3
J3,4
54.5
55.6
55.6
56.6
JF,~
JF,Z
JF,~
JF,~
JF,S
JF,6
JF.6'
6F
S
References
1,6-Anhydro-2-deoxy-2-fluoro-/3-~-glucopyranose 3,4-di-O-acetyl5.51 4.24 5.00
4.64
4.64
C
118,119
17.0 45.0 3-0-acet yl-4-0-benzyl5.51 4.25 5.14
3.25
4.60
C
118,119
3.35 1.4
4.4-4.7
C
I20
45.0 17.0 3,4-di-O-benzyl5.53 4.35 3.6-3.8 I .4 4.9 45.0
3.6-3.8 1.2
3.91 1.3
2-O-Acetyl-1,6-anhydro-4-O-benzyl-3-deoxy-3-fluoro-/3-~-~tropyranose 5.52 1.5
6.5
5.23 9.0 13.0
4.78 4.5 48.0
3.9-3.99
4.65
C
118,119
2,4-Di-0-acetyl-1,6-anhydro-3-deoxy-3-fluoro-/3-~-idopyranose
-202.1 c 0.0 4.5 8.0 0.0 4.5 4.5 1,6-Anhydro-3-deoxy-3-fluoro-/3-~-mannopyranose 5.43 3.83 4.74 4.12 4.63 4.09 3.81 D 1.9 4.5 2.0 2.0 1.2 6.0 1.9 0 26.4 47.1 12.5 0.8 1.4 3.8 2,4-di-O-acetylC 5.49 4.15-5.01 5.04 4.65 4.20 3.88 1.6 1.8 I .2 5.9 1.9 0.0 12.6 0.0 1.3 3.5 3-~-Acetyl-1,6-anhydro-2,4-dideoxy-/3-~-glucopyranose 4-acetamido-2-fluoro5.52 4.27 4.84 4.10 4.50 4.19 3.80 C 2.5 1.5 1.5 2.5 I .o 6.0 8.0 1.0 43.0 15.0 2-acetamido-4-fluoro5.34 3.99 4.86 4.29 4.56 3.89 3.65 1.5 1.5 1.5 1.5 1.5 5.0 8.0 1.5 15.5 45.0 11.0 1.5 5.0 1,6-Anhydro-2,4-dideoxy.2-fluoro-/3-~-e~~~~o-hexop~anos-3-ulose 4.63 4.20 2.91a 2.40e 4.83 3.75 3.64 N 1.9 5.6 I .3 0.5 4.0 7.8 2.0 49.0 2.0 4.5
8.0 16.0
8.0 50.0
12
4.5 16.5
I
73 h
73
121 c
6,121 P
122
r.Y
For the nonacetylated derivative, a shift of 6F = -198.2 for a solution in D was reported. Also reported, in C. ' J (H-I, H-3)= 1.50, J (H-2, H-4) = 1.0, J (H-3, H-5) = 1.5 Hz. Solvent: 5 : 1 : 1
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
I IS
chloroform-dimethyl sulfoxide-hexafluorobenzene. J (H-I, H-3) = 1.5, J (H-1, H-5) = 1 .O Hz. f J (H-4, H-4') = 17.7 Hz. The symbol a stands for the axial, and e for the equatorial, proton at C-4.
(118) J. Paciik, J. PodeSva, Z. ToCfk, and M. (?ern$, Collect. Czech. Chem. Commun., 37 (1972) 2589-2599. (119) J. Pachk, Z. ToEfk, and M. Cernf, Chem. Commun., (1969) 77. (120) T. Haradahira, M. Maeda, Y. Kai, and M. Kojima, J . Chem. Soc., Chem. Commun., (1985) 364-365. (121) J. Pacak, P. DraSar, D. Stropovit, M. Cern$, and M. BudCSinsk$, Collect. Czech. Chem. Commun., 38 (1973) 3936-3939. (122) J. DoleZalovB, M. Cerny, T. Tmka, and J. Pacak, Collect. Czech. Chem. Commun., 41 (1976) 1944-1953. TABLEXXII 'H- and 19F-N.m.r.Data for Fluorinated 3,6-Anhydrohexose Derivatives Compound H-2 H-1
H-3
H-4
H-5
H-6
H-6'
J1.2
J2,3
53.4
54,s
55,6
55,6'
56.6'
JF.1
JF,Z
JFJ
JF,~
JFJ
JF,~
Jv.6
2-0-Acetyl-3,6~nnhydro-S~O-benzoyl-~-idofuranosyl fluoride a anomer
6F
S
-138.0
A
p anomer 5.72 5.28 5.06 4.72 5.56 4.42 4.06 -119.8 A 0.8 0.5 4.8 1.0 4.0 1.5 10.6 62.3 5.8 0.5 4.8 1.5 3,6-Anhydro-5.deoxy-S-fluoro.1,2-~-isopropylidene-~-~-glucofuranose -207.6 B 1.6" 5.8O 51.6 19.5 3,6-Anhydro-5-deoxy-S-fluoro-~-idofuranose 1 ,2-di-Qacetyla anomer 4.28 4.93 5.14 5.10 4.68 6.12 1.0 0.5 3.0 0.5 4.6 0.5 39.8 10.8 50.6 2.7 0.5 1.0 p anomer 5.08 3.91 4.97 6.34 4.94 4.88 0.5 2.8 0.8 0.5 3.3 4.4 50.6 38.1 8.1 0.5 1.0 2.0 1,2-O-isopropylidene-p4.70 3.59 4.71 4.32 4.59 5.59 0.5 2.8 0.8 0.5 3.2 3.5 38.3 7.5 50.4 0.5 1.5 1.5 a
References
22
22
92,123
17.9
4.00 11.4 25.5
-186.7
A
92
4.08 11.6 22.3
-190.8
A
92
3.75
-189.7
B
92
11.1
26.1
Assignments may have to be reversed.
(123) R. Csuk and B. I. Glanzer, unpublished results.
RENE CSUK AND BRIGITTE I. GLANZER
116
IH-
TABLEXXIII and I9F-N.m.r. Data for Fluorinated Sugar Acids and Lactones
(D-Glucofuranosylfluoride)urono-6,3-lactone 2,S-di-O-acetyl-P5.91 5.35 5.23 5.36 5.63 0.6 0.5 4.6 6.3 60.1 4.5 0.5 4.4 0.5 2,S-di-O-benzoyl-P6.2 5.7 5.56 5.71 5.98 0.5 0.5 4.6 6.3 60.1 4.0 0.5 4.6 0.3 ~-Deoxy-3-fluoro-~-gluconic acid
-118.3
A
22 a
-118.5
A
22 a
-207.0
D
70
Methyl (methyl 4-deoxy-4-fluoro-cu.~-glucopyranosid)uronate -119.2
M
124
14.7
54.5
5-Deoxy-5-fluoro-1,2-O-isopropylidene-cu-~-glucofuranurono-6,3-lactone 6.08 3.6
4.87 4.90 5.08 5.33 -216.3 C 91 0.6 2.8 4.0 b 3.5 I .3 1.0 48.0 5-Deoxy-5-fluoro-&~-idofuranurono-6,3-lactone 1,2-O-benzylidene6.17 5.09 5.40 5.22 5.09 -199.0 c 125 3.6 0.0 4.0 0.0 0.0 10.0 47.5 I ,2-O-isopropylidene5.95 4.87 5.10 4.96 4.93 -199.7 C 91 3.7 3.3 0.4 1.2 8.7 48.3 Methyl [benzyl 2-(benzyloxycarbonyl)amino-2,3,4-tndeoxy-5-fluoro-~-~-e~~~ro-hex-3enopyranosid]uronate 4.88 4.75 5.75 5.46 B 126 3.5 10.0 d 1 .O 1 .O " J (H-3, H-5) = 0.5 Hz. * J (H-2, H-4) = 0.5 HZ. ' J (H-3, H-5)= 0.4, J (H-2, H-4) = 0.3 Hz. Assignments of H-3 and H-4 may have to be reversed; some values were also given for C as the solvent.
(124) J. Samuel and N. F. Taylor, Carbohydr. Res., 133 (1984) 168-172. (125) R. Albert, K. Dax, U. Katzenbeisser, H. Sterk, and A. E. Stiitz, J. Carbohydr. Chem., 4 (1985) 521-528. (126) J. Kiss, P. C. Wyss, G. Flesch, W. Arnold, K. Noack, and P. Schonholzer, J . Carbohydr. Chem., 4 (1985) 347-361.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
I 17
TABLEXXIV IH- and UF-N.m.r. Data for Aminodeoxyhexopyranosyl Fluorides (and Their Synthetic N-Containing Precursors) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JLZ
JZJ
J3,4
J~J
55.6
5 5 , ~
56.6
JFJ
JF,Z
JFJ
JF.4
JFJ
JF,6
JF,~
3-Azido-4,6-0-benzyldene-3-deoxy-~~-allopyranosyl fluoride 5.53 8.0 52.0
3.50 3.5 12.5
4.20 3.0 3.4
3.60 9.0
3.99 9.0
3.72 5.0
4.37 9.0
-147.3
2-Acetamido-2-deoxy-~-~-glucopyranosy~ fluoride 5.18 7.8 54.0
11.0 3,4,6-tri-O-acetyl5.39 6.8 53.0 13.0
S
References
C
I27
M
128
C-M
128
(127) S. Castillon, A. Dessinges, R. Faghih, G. Lukacs, A. Olesker, and T. T. Thang, J. Org. Chem., 50 (1985) 4913-4917. (128) F. W. Ballardie, B. Capon, W. M. Dearie, and R. L. Foster, Carbohydr. Res., 49 (1976) 79-92.
TABLEXXV 'H- and "F-N.m.r. Data for 3-Amino-2,3-dideoxy-2-fluoro-a-~-altropyranoside Derivatives (and Their N-Containing, Synthetic Precursors) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JI,Z
52.3
53.4
J4.5
55.6
5 5 , ~
36.6
JFJ
511.2
JFJ
JF,~
JF,~
JF,~
JF,~
SF
4,6-0-Benzylidene-2,3-dideoxy-2-fluoro-a-~-~tropyranoside methyl 3-amino4.77 4.66 3.57 -189.2 0.2 2.6 2.6 9.8 43.8 11.6 benzyl 3-azido4.90 4.63 4.29 4.09 4.29 3.77 4.29 -190.8 0.0 2.5 4.0 9.5 10.5 10.5 11.5 43.5 11.5 3.0
S
References
C
129
C
127
(continued)
TABLEXXV (continued) Compound
S
References
3.92 10.0
C
128
4.29
C
127
H-1
H-2
H-3
H-4
H-5
J2,3
J3.4
J4,a
$5.6
H-6 Js,~
H-6’
JIS JFJ
JF,Z
JFJ
JF.4
JF,S
JF.~
JF,~
4.17 10.0 2.5
4.11 4.0
4.37 10.0
benzyl 3-benzarnido5.12 4.77 5.14 1.0 4.5 44.0 8.5
6F
56.6‘
Benzyl2,3-dideo~y-2-fluoro-cu-~-altropyranoside 3-azido-6-O-he .~ thvlsulfonvl)4.92 4.67 4.04 4.17 2.0 12.0 43.0 3-benzarnido5.42 5.14 5.51 4.81 4.34 1.0 4.0 9.5 44.0 3-benzamido-6-0-mesyl5.19 4.72 4.97 4.2-4.00 1.0 4.0 1.5 7.5 45.0
4.46
10.0
-
4.60
P
128
4.64
4.49 11.0
C
128
C
128
C
I30
5.5
3-benzarnido-6-O-tos yl-
4.45 4.20 5.06 4.62 4.87 4.03-3.95 1.0 3.0 1.5 11.0 10.0 8.0 45.0 Methyl 3-benzamido-2,3-dideoxy-2-fluoro-cu-~-al~opyranoside 4,6-di-O-acetyl4.92 4.60 5.13 5.18 4.12 4.25 - 193.3 1.5 3.5 4.5 10.0 4.0 4.0 8.0 45.0 8.6 1.5 4,6-di-O-benzoyl5.00 4.67 5.35 5.63 4.40 4.67 4.47 -193.7 1.5 3.6 4.6 9.6 2.6 6.0 12.0 8.0 44.0 9.0 2.0 4,6-O-benzylidene4.85 4.29 5.06 3.87 -191.4 2.5 9.0 1.5 3.0 8.5 1.0 9.0 45.0 Methyl 4,6-0-benzylidene-2,3-dideoxy-2-fluoro-cu-~-al~opyranoside 3-(diallylarnino)4.70 - 182.6 18.5 13.0 42.5 3-(trifluoroacetarnido)4.89 4.66 4.89 1.4 3.0 4.5 7.5 45.0 7.5
4.32 9.8
3.95 4.2
“ J ( H - I , H-3) = 1.2 Hz. b J ( H - l . H-3)
=
4.08 9.8
3.85 9.8
1.5 Hz. ‘J(H-1, H-3)
-191.6
=
1.5 Hz.
‘ I
C
130 b
C
130 c
C
131
C
131
I I9
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
(130) L. Hough, A. A. E. Penglis, and A. C. Richardson, Carbohydr. Res., 83 (1980) 142- 145. (131) D. Picq and D. Anker, J . Carbohydr. Chem., 4 (1985) 113-123. TABLEXXVI 'H- and 19F-N.m.r. Data for Aminodideoxy-3(or 4)-flUOrO Sugars (and Their N-Containing Synthetic Precursors)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JI,~
J2.3
53.4
J4.5
55.6
JS,C
56.6,
JFJ
JFJ
JF,3
JF,4
JF.5
JF.6
JF,C
6F
Methyl 6-azido-3,6-dideoxy-3-fluoro-~-~-allopyranoside 4.52 3.47 4.89 3.61 3.84 3.48 3.48 -217.4 10.0 8.5 2.0 2.0 2.0 29.0 53.0 28.0 4,6-0-Benzylidene-2,3-dideoxy-3-fluoro-a-~-glucopyranoside benzyl 2-acetamido5.05 3.88-3.97 4.78 3.88-3.97 4.28 3.85 4.0 9.0 10.0 4.0 10.0 10.0 60.0 2.0 benzyl 2-azido5.03 3.47 5.03 3.78 3.91 3.78 4.26 -198. 10.0 4.0 9.0 9.0 9.0 9.0 4.5 5.5 9.0 54.5 2.0 methyl 2-benzamido4.89 4.43 4.97 4.05 3.72 4.28 3.87 3.7 9.8 9.4 9.0 4.8 10.3 10.0 3.0 12.1 53.6 12.4 0.7 1.9 Methyl 3,6-di-0-ace:etyl-2,4-dideoxy-4-fluoro-a-~-glucopyranoside 2-acetamido4.67 5.30 4.70 -199.8
S
References
A
65
C
132
C
I27
S
133
P
134
14.7 49.7 2-benzamido4.83 4.42 5.48 4.59 4.42 4.44 -196.9 C I34 3.3 11.3 9.7 9.7 1.8 11.3 3.3 13.0 49.7 4.4 Benzyl 2-acetamido-3-O-ace:etyl-2,4-dideoxy-4-fluoro-6-O-tn:etyl-a-~-g~opyranoside 5.05 -188.2 C 135 4.0 54.0 Methyl 4,6-dideoxy-4-fluoro-a-~-talopyranoside 6-azido4.87 4.70 3.93 3.35 3.68 -216.1 A 65 0.0 5.0 8.0 12.0 51.0 30.0 2.0 (I
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
120
TABLEXXVI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
Jl,Z
J2,3
J3.4
J4,S
55.6
J5.6'
56.6'
JF,~
JFJ
JFJ
JF.4
JF,S
JF,~
JF.6'
3.68
4.67
3.90
3.37
6-amino4.69 3.64 0.0
32.0
51.0
3.37
6F
S
References
-217.0
A
65
31.0
Data also reported for P as the solvent.
(132) L. H. B. Baptistella, A. J. Marsaioli, J. D. De Souza Filho, G. G. De Oliveira, A. B. DeOliveira, A. Dessinges, S. Castillon, A. Olesker, T. T. Thang, and G. Lukacs, Cnrbohydr. Res., 140 (1985) 51-59. (133) H. H. Baer and A. Jaworska-Sobiesiak, Cnrbohydr. Res., 140 (1985) 201-214. (134) L. Hough, A. A. E. Penglis, and A. C. Richardson, Cnn. J . Chem., 59 (1981) 396-405. (135) M. Sharma and W. Korytnyk, Cnrbohydr. Res., 79 (1980) 39-51. TABLEXXVII 'H- and I9F-N.m.r. Data for Aminodideoxy-6-luoro Sugars
2-Acetamido-l,3,4-tri-O-acetyl-2,6-dideoxy-6-fluoro-~-gda~opyranose -230.8 C 18.5 47.5 47.5 Methyl 2,6-dideoxy-6-fluoro-cu-~-gdactopyranoside 2-acetamido15.8
2-acetamido-3,4-di-O-acetyl4.78 5.16 5.38 3.5 11.0 3.2 1.0
47.5
-235.0
P
134
-238.0
C
134
-234.9
C
134
-236.2
C
134
47.5 4.40
46.0
85
46.0
2-benzamido14.5
3,4-di-O-acetyl-2-benzamido-
4.98 3.5
10.0
5.29 3.5
5.50
1.0
46.0
46.0
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
121
TABLEXXVII (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.2
J2,3
53.4
54,s
55.6
55.6
J6.6,
JF,l
JFJ
JFJ
JF,~
JFJ
JF,6
JF,~
2-benzamido-4-0-benzo yl-3-0-benzyl-
5.03 3.3
10.5
3.80 3.2
5.84 1.3
2-benzamido-3-O-benz yl-
14.5 48.5 48.5 2-Acetamido-2,6-dideoxy-6-fluoro-~-glucopyranose a anomer 5.86 5.26 4.18 3.2 2.7 29.3 48.1 48.7 I ,3,4-tri-O-acetyla anomer 6.17 4.44 3.97 4.42 3.5 25.0 48.5 48.5 p anomer
SF
S
-236.2
C
134
-235.2
C
134
-238.0
P
134,136
-238.0
C
85,134
-232.5
C
85
P
85,136
21.8 48.2 48.2 2-Acetamido-2,6-dideoxy-6-fluoro-cu-o-glucopyranoside benzyl 3,4-di-O-benzyl-232.8 5.21 5.02 4.55 3.6 2.5 29.0 47.5 47.5 methyl 3,4-di-O-acetyl-236.1 3.64 4.46 4.14 4.32 5.06 5.16 3.5 10.0 10.0 10.5 23.5 48.5 48.5 methyl 3,4-di-O-methyl-233.4 4.92 4.41 4.95 3.4 2.4 27.5 48.0 48.0 Methyl 2-benzamido-2,6-dideoxy-6-fluoro-a-~-glucopyranoside -239.0 26.0 3,4-di-O-acetyl4.87 4.51 5.40 3.5 10.0 10.0
5.12 10.0
49.5
3.98 23.5
a
P
134
P
136
A
134
A
134
49.5 4.46
48.5
References
-237.4
48.5 (continued)
RENB CSUK AND BRIGITTE I. GLANZER
I22
TABLEXXVII (continued) Compound H-1 H-2
6F
S
References
-239.1
C
134
-231.8
C
134
A
65
A
65
D
1 I6
-237.3
D
I I6
4.95
-234.1
s
1I6
1,3,4-tri-O-acetyla anomer 5.19 1.6
-234.3
C
85,116
-233.1
C
85,116
H-3
H-4
H-5
H-6
H-6'
J1.2
JZJ
J3,4
54,s
Js,6
55.6'
J6,v
JF.1
JF,~
JFJ
Jp.4
Jp.5
JF,~
JF,6'
3-0-benzyl28.0
49.5
49.5
3-0-benzyl-4-O-mes yl-
22.5 41.4 41.5 Methyl 4,6-dideoxy-6-fluoro-cu-~-glucopyranoside 4-azido4.14 3.50 3.60 4.60 4.60 -234.1 10.0 3.5 26.0 46.0 46.0 4-amino4.1 3.92 4.25 4.33 -233.8 4.0 10.0 4.0 1.5 10.0 28.5 48.0 48.5 2-Amino-2,6-dideoxy-6-fluoro-~-mannopyrmose hydrochloride (I anomer -231.5
p anomer
21.9
21.5
45.9
41.0
45.9
41.0
2-Acetamido-2,6-dideoxy-6-fluoro-~-mannopyranose
p anomer
25.5
41.2
41.2
6.01 1.8
23.8
41.5
41.5
Ref. 85 reported J (H-5, F) = 22.5 Hz.
(136) M. L. Shulman and A. Ya. Khoriin, Carbohydr. Res., 21 (1913) 141-141.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
123
TABLEXXVIII 'H- and I9F-N.m.r. Data for 3-Amino-2,3,6-trideoxy-2-fluoro-6-halogeno-cr-~altropyranoside Derivatives (and Their N-Containing Synthetic Precursors)
Benzyl 2,3,6-trideoxy-2-fluoro-6-iodo-a-~-altropyranoside 3-azido4.88 4.61 3.71 4.06 3.45 3.21 C 121 3.0 10.5 10.5 2.5 11.0 12.0 44.0 3-benzamido5.20 4.10 4.92 3.99 3.87 3.16 3.32 C 132 1.0 3.5 2.5 10.0 2.0 9.0 11.0 1.5 43.0 2.0 Methyl 4-0-benzoyl-6-bromo-2,3,6-trideoxy-2-fluoro-cr-~-altropyranoside 3-benzamido5.03 4.70 5.30 5.40 4.25 3.61 3.51 C 132,133, 1.5 3.5 4.0 10.0 2.4 8.2 10.9 137 8.0 44.5 9.0 2.0 3-(trifluoroacetamido)4.99 4.63 5.03 5.38 4.16 3.60 3.5 -204.0 C 131 10.8 8.0 1.3 3.0 4.3 10.8 2.5 1.7 44.3 1.7 (137) M. K. G u j a r , V. J. Patil, J. S. Yadav, and A. V. Rama Rao, Carbohydr. Res., 135 (1984) 174-177. TABLEXXIX 'H- and I9F-N.m.r. Data for 3-Amino-2,3,6-trideoxy-2-fluoro-hexopyranoside Derivatives (and Their N-Containing Synthetic Precursors) Compound H-1 H-2 Jls J2.3 JF.1
JF,2
H-3
H-4
H-5
H-6
H-6'
J3c
J4,5
554
J5,6'
J6.6
JFJ
JF.4
JFJ
JF.6
J F . ~
SF
Benzyl 3-benzamido-2,3,6-trideoxy-2-fluoro-cr-~-altropyranoside 4.65 4.12 4.97 3.91 3.83 1.43 2.0 2.0 7.0 8.0 45.0 Methyl 2,3,6-trideoxy-2-fluoro-a-~-altropyranoside 3-amino4.75 4.57 3.45 3.26 3.60 1.34 1.6 3.2 10.0 6.2 10.2 45.5
S
References
C
132
C
133 a
(continued)
RENB CSUK AND BRIGITTE I. GLANZER
124
TABLEXXIX (continued)
Compound
H-1
H-2
H-3
H-4
H-5
H-6
H-6'
JIJ
J2.3
J3,4
J4.5
55.6
J5.6,
564'
JF.1
JF.2
JFJ
JF,~
JFJ
Jw.6
JF,~
5.28 9.8 2.0
4.16 6.3
3.83 9.0
3.76 6.6
3-benzamido-4-O-benzo y l-
4.92
4.67 5.23 3.2 4.0 8.0 45.3 8.5 3-(trifluoroacetamido)4.84 4.60 4.13 1.5 3.5 4.5 7.8 45.0 9.0 1.5
SF
S
C
1.32
References
133 137 0
I .36
C
133 0
2,3,6-Trideoxy-2-fluoro-~-galactopyranose 3-amino-, hydrochloride (I! anomer 5.29 4.15 3.74 3.83 4.21 1.18 -192.2 3.5 10.5 3.5 1.0 6.5 0.0 50.4 11.0 p anomer 4.15 4.40 3.55 3.83 3.76 1.25 -192.4 7.7 10.0 3.5 6.5 3.0 52.0 11.2 I -O-acetyl-4-O-benzoyl-2-fluoro-3-(tnfluoroacetamido)-~5.90 4.70 4.60 5.63 4.13 1.26 8.0 10.0 2.0 1.0 7.0 4.0 45.0
M
131
M
131
C
121
Benzyl2,3,6-trideoxy-2-fluoro-/3-~-g~lactopyr~noside 3-amino4.85 4.77 7.0 8.0 8.0 52.0 3-benzamido4.30-4.60-
3.15 4.0
3-(trifluoroacetamido)4.63 4.37 3.75 7.5 9.0 9.0 51.0
3.78 7.0
1.47
C
127
3.24
2.98 7.0
0.94
B
132
4.29
3.18 7.0
1.33
C
127
C
127
C
133
3.88 3.0
4-O-benzoyl-3-(trifluoroacetamido)-
4.71 4.57 4.49 5.52 3.90 1.24 7.0 10.0 3.0 7.0 5.0 8.0 54.0 Methyl 2,3,6-trideoxy-2-fluoro-~-galactopyranoside 3-amino-P4.36 4.17 3.02 3.62 3.68 1.35 7.6 9.5 3.0 1.0 6.5 3.3 51.0 13.0 3.0
-193.4
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
I25
TABLEXXIX (continued) Compound H-1 H-2
6F
References
H-3
H-4
H-5
J1.z
J2.3
53.4
J4.5
55.6
H-6 H-6' 5 5 , ~ 56.6
JFJ
JF.~
JFJ
JFP
JF,5
JF,6
3.82
4.32 7.0
1.32
C
132
5.65 1.0 2.0
4.05
1.27
c
133,137
3.81 3.0
3.9 6.4
1.26
A
131
3.81
3.90 6.4
1.26
C
133
3-benzamido-P4.50-
JF.6'
3-benzamido-4-O-benzoyI-p4.62 4.55 4.80 7.4 10.7 3.7 3.0 52.9 12.5 3-(trifluoroacetamido)a anomer 4.52 4.45 4.27 7.3 10.0 3.0 6.8 51.0 10.0 P anomer 4.55 4.46 4.30 7.4 10.4 3.1 0.5 50.7 13.5
1.1
3.1
6.4
S
b
"JJH-I, H-3) = 1.5 Hz. Ref. 137 reported couplings: J (H-I, H-2) = 10.5 andJ(H-2, H-3) = 8.0 Hz.
TABLEXXX 'H- and I9F-N.m.r. Data for Amino-2,3,6-trideoxy-2-fluorohexo-pyranosides, -pyranoses, and -pyranosyl Halides Compound H-1 H-2
H-6'
H-3
H-4
H-5 H-6
51.2
J2.3
J3,4
54,s
55.6
35.6
J64'
JFJ
JF,~
JFJ
JF,~
JF,S
JF.6
JF,~
SF
S
References
4-0-Benzoyl-2,3,6-tndeoxy-2-fluoro-3-(tnfluoroacetamido)-~~-gala~opyranosyl bromide 6.68 4.78 4.93 5.63 4.50 1.23 C 127 4.0 10.0 7.0 50.0
6-Azido-QO-benzoyl-2,3,6-tndeoxy-2-fluoro-~-ribo-hexopyranosyl halide chloride a anomer 6.25 4.86 2.31/2.66 5.11 4.31 3.36-3.62 C 3.8 12.0/5.0 11.Y5.0 10.0 5.0 3.0 48.0 p anomer 5.55 4.65 6.5 9.015.0 4.5 48.0
855.0
1.5
2.0/2.88 9.0/5.0 13315.0
5.16 8.0
4.00
3.36-3.62
C
138 a. b
138 o.e
1.0
(continued)
I26
RENE CSUK AND BRIGITTE I. GLANZER TABLEXXX (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6’
Jl.2
J2.3
53.4
J4,5
55.6
Js.6,
56,6’
JFJ
JF,Z
JF$
JF.4
JF,~
JF.6
JF.6,
4.65 11.Y4.7
2.32/2.64
4.28 5.0
2.7
47.5
8.3/5.0
5.14 10.0 1.4
3.94
2.20/2.57
5.16 11.5 1.4
4.05 5.0
2.7
6.61 3.8
7.05 4.0 2.0
a bromide
a iodide
11.5/5.0
11.Y5.0
11.Y5.0
6F
S
References
3.49 13.5
C
138
3.49 13.5
C
o.d
138 a.e
8.Y5.0 47.5 6-Azido-4-O-henzoyl-2,3,6-trideox~2-fluoro-~-ribo-hexopyranose a anomer
5.44 3.8 1.0
4.70 2.2Y2.59 5.02 4.30 3.31-3.50 -190.5 C 12.0/5.0 11.515.0 10.0 48.0 9.0/5.5 1.2 p anomer 4.93 4.40 1.91/2.81 5.02 3.88 3.31-3.50 -190.2 C 7.0 11.0/5.0 11.Y5.0 10.0 3.0 49.0 12.0/7.0 1.2 Methyl 6-~do-4-O-henzoyl-2,3,6-trideoxy-2-fluoro-~-~-ribo-hexopyranoside 4.10 4.11 1.47/2.35 4.71 C 7.2 10Y5.2 10Y5.0 3.5 48.0 12.Y7.0
138 a.f
138 a.g
138 ash
Shifts and couplings for axial (a) and equatorial (e) proton, respectively. J (H-3a. H-3e) = 11.5, J (H-I, H-3e) = 0.5 Hz. J ( H - ~ uH-3e) , = 13.5 Hz.d J (H-I, H-5) = 0.3, J (H-I, H-3e) = 1.3, J (H-3a, H-3e)= 11.5Hz.’J(H-l,H-3e) = 1.5Hz.’J(H-l,H-3e)=0.3;J(H-l,OH)= 3.5,J(H-3a,H-3e)= , = 12.0 Hz. 11.5 Hz. g J (H-I, OH) = 5.0, J (H-3a, H-3e) = 12.0 Hz. J ( H - ~ uH-3e) @
(138) T. Tsuchiya, Y.Takahashi, M. Endo, S.Umezawa, and H. Umezawa, J . Carbohydr. Chem., 4 (1985) 587-61 1.
TABLEXXXI ‘H- and 19F-N.m.r. Data for Fluorinated Unsaturated Amino Sugars Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6‘
Jl.2
JZS
J3.4
J4,s
55.6
55.6
J6.6
JF.1
JFJ
JFJ
JF.~
JF,5
Jp.6
JF,6’
6F
S
References
2,3,6-Trideoxy-2-fluoro-a-~-arabino-hex-5-enopyranoside
benzyl 3-azido4.67 4.62 3.11 4.0 7.0 3.5 11.0 47.0 12.5
3.94
4.66
4.44
C
127
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
127
TABLEXXXI (continued) Compound H-1 H-2
H-3
H-4
H-5
52.3
J3,4
54.5
55.6
H-6 55.6
H-6'
J1,Z
SF
JFJ
JFJ
JFJ
JF,~
JFJ
JF.6
JF.~
S
References
56,6
benzyl 3-benzamido5.10 4.81 5.18 4.90 B 4.74 4.25 132 1.0 2.5 8.0 45.0 methyl 3-benzamido4.92 4.75 4.68 4.92 4.92 132 C 1.0 3.5 44.0 methyl 3-benzamido-4-0-benzoyl132,133 5.03 4.86 5.24 5.98 4.97 4.83 C 2.0 4.0 4.8 1.5 137 8.0 46.0 8.0 3.3 methyl 4-O-benzoyl-3-(trifluoroacetamido)4.33 6.0 -193.7 c 131 1.7 3.3 3.7 7.3 47.0 7.3 1.7 Methyl 3-benzamido-2,3,4,6-tetradeoxy-2-fluoro-~-~-~~reo-hex-4-enopyranoside 4.84 4.66 4.77 I37 5.11 I .85 C 1.5 3.5 9.0 46.0 Methyl 2-benzamido-3-O-benzyl-2,4,6-trideoxy-6-fluoro-~-~-~~reo-hex-4-enopyr~oside -224.1 C I34 (1
48.0 " J (H-I, H-3)
=
48.0
1.5 Hz.
TABLEXXXII 'H- and IgF-N.m.r. Data for Fluorinated Aminodeoxyhexo-furanosesand -furanosides Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
Ji.2
52.3
534
54.5
55.6
Js,~
J6,6'
JF,I
JFJ
JF.~
JF,~
JF.S
JF,~
JF,~
3,6-Dideoxy-~~-galactofuranosyl fluoride 3-azido-5-0-benzoyl-2-0-benzyl5.83 3.95-4.605.40 6.4 59.3 3-azido-5-O-benzoyl-2-O-methyl5.74 3.95 3.78 4.24 5.36 3.0 6.2 4.2 6.2 60.0 10.5 1.8 ~
S
References
1.41
C
139
1.42
C
139
6F
(continued)
RENfi CSUK AND BRIGITTE I. GLANZER
128
TABLEXXXII (continued) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6’
51.2
J2J
J3.4
54,s
55.6
55.6’
J6,6#
JFJ
JF,Z
JFJ
JFC
JF,S
JF.6
JF.~
SF
S
References
5-O-benzoyl-2-O-rnethyl-3-(trifluoroacetarnido)5.87 3.92 4.35-4.58 5.42 1.43 C I39 4.0 7.0 60.0 7.0 5-O-benzoyl-2-O-benzyI-3-(tri~uoroacetarnido)5.83 4.04 4.52 4.37 5.39 1.42 C 139 1.O 4.8 2.0 6.6 59.4 7.2 3-Acetamido-2,3,5,6-tetradeoxy-5-luoro-l-O-(4-nitrobenzoyl)-~,~-~~-~~~o-hexofuranose 6.65 2.212.7 4.7 4.13 4.75 1.43 C 140 4.9 8.0 2.0 2.7 6.6 b 24.6 48.7 23.9 Methyl 3-acetamido-2,3,5,6-tetradeoxy-5-luoro-~~~-ri~o-hexofuranoside 5.14 1.7-2.3 4.55 3.86 4.71 1.34 C 140 2.0 3.0 6.4 24.2 24.7 56.0 (1
a
’
J (N-H, H-3) = 9.0 Hz. J (H-2, H-2’) = 14.1 Hz.
(139) A. Hasegawa, M. Goto, and M. Kiso, J . Carbohydr. Chem., 4 (1985)627-638. (140) J. T. Welch, B. M. Svahn, S . Eswarakrishnan, J. P. Hutchinson, and J. Zubieta, Carbohydr. Res., 132 (1984)221-231. TABLEXXXIII ‘H- and IgF-N.m.r. Data for Fluorinated Aminodeoxypentopyranosides Compound H-1 H-2
H-3
H-4
H-5
H-5’
Ji.2
JZJ
J3.4
J4,5
54.5’
Js,s*
JFJ
JFJ
JFJ
JF,~
JF.S
JF,s’
6F
S
Methyl 4-~-~yl-2-amino-2,3-dideoxy-3-fluoro-~~-arabinopyranoside 4.80 3.25 4.65 -198.9 C 3.9 10.0 3.9 10.0 49.1 Methyl 2-amino-2,3,4-trideoxy-3.luoro-f~reo-pentopyranoside (Y-L4.75 2.8 4.5 -187.7 C
3.7 3.7
9.3 11.7
References
129
129 a
51.3
14.117.5
p-D-
4.0 7.3
2.85 9.0 12.0
4.45 9.016.0 50.5
Couplings for the axial and equatorial proton, respectively.
-186.0
C
129 n
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
IH-
TABLEXXXIV and I9F-N.m.r. Data for 2-deoxy-2-halogeno-hexopyranosyl Fluorides
3,4,6-Tri-0-acetyl-2-deoxy-~-galactopyranosyl fluoride 2-bromoa anomer 50.5 25.1 p anomer 10.0 49.7 2-iodoa anomer 50.0
8.0 9.0 50.3 10.0 2-chloroa anomer
34,141
- 135.6
34
-139.4
34
-130.8
34
- 144.9
34,40, 141,142, 143,"
- 136.0
15.34, 40
3.94
- 147.6
40,144
3.47
- 138.9
40,144
- 139.8
34,40, 142,143
24.0
p anomer
51.0 10.6 2-iodoa anomer
2.4 50.5
- 145.0
27.6
p anomer
49.8 10.2 3,4,6-Tri-0-acetyl-2-deoxy-~-glucopyranosyl fluoride 2-bromoa anomer 5.8 2.5 9.0 9.0 9.0 51.5 25.2 /3 anomer
51.2
I29
11.0 27.8
b
(continued)
RENB CSUK AND BRIGITTE
I30
I. GLANZER
TABLEXXXIV (continued)
49.9 9.3 3,4,6-Tri-0-acetyl-2-deoxy-~-mannopyranosylfluoride 2-bromoa anomer
1.5 50.2
4.0 2.8 p anomer 5.95 I .8 52.0 2-chloroa anomer
C
14,15 34,40 141.143'
C
142,145
-127.8
B
40,144
-118.6
C
144
-116.9
A
34,40, 141,143
-123.2
9.5
3.92 3.6 49.5 2.0 p anomer 49.4 3.6 2-iodoa anomer
I .5
4.3 51.7 *3.9 p anomer 5.95 I .8 52.0
9.5
d
142
3,4,6-Tri-0-acetyl-2-deoxy-~-talopyranosyl fluoride 2-bromo-a-
-121.4
C
34
-114.6
C
34
49.8 4.6 2-iodo-a50.5
6.3
nJ(H-1,H-3)=0.4Hz.bJ(H-I,H-3)=0.2,J(H-l,H-5)=0.2Hz.LJ(H-2,H-4)=0.3Hz.dRef.
reported 4.3 Hz,whereas Ref. 141 reported 1.0 Hz,in addition: J (H-I, H-3)= 0.5,J (H-2, H-4)= 0.5, J (H-1, H-5)= 0.2 Hz.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
131
(141) J. C. Campbell, R. A. Dwek, P. W. Kent, and C. K. Prout, Carbohydr. Res., 10 (1969) 71-77. (142) K. R. Wood, P. W. Kent, and D. Fisher, J . Chem. Soc., C , (1966) 912-915. (143) L. D. Hall and J. F. Manville, Carbohydr. Res., 8 (1968) 295-307. (144) L. D. Hall and J. F. Manville, Can. J. Chem., 47 (1969) 379-385. (145) J. C. Campbell, R. A. Dwek, P. W. Kent, and C. K. Prout, Chern. Commun., (1968) 34-35.
TABLEXXXV 'H- and IgF-N.m.r. Data for 2-Deoxyhexopyranosyl Fluorides and 2,3-Dideoxy-2-fluoro-hexopyranosides Compound H-1
H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
JZJ
53,4
54,s
55.6
55.6
56.6'
JF,I
JF.Z
JFS
JF,~
JF,S
JF,~
JF,~
4.34 4.5
4.09 -131.1 12.8
2-Deoxy-~-arabino-hexopyranosyl fluoride 3,4,6-tri-O-acetyla anomer 5.76 2.43/1.86~ 5.32 5.08 4.14 1.6/2.850 5.2/10.8 9.5 2.0 51.2 5.0/38.0 9.5 p anorner
6F
S References
C
14,15, 33,34,40 n.6
-125.2
c
40 (I
15.3d10.7e 3,4,6-tri-O-benzoyl-a5.82 2.7512.07~ 5.72 1.5/2.5a 51.1 5.3/38.3 2-Deoxy-D-lyxo-hexopyranosyl fluoride 3,4,6-tri-O-benzoyl-a6.01 2.80/2.0a 5.76 6.00 2.0/2.5a 11 3 6 . 0 1.0 3.0 51.0 3,6-di-O-benzoyl-a5.88 2.0-3.0 5.50 2.0/2.0 11.5/5.5 3.0 52.0 4,6-di-O-benzoyl-a5.93 1.8-2.7 4.2-4.7 5.68 2.012.0 3.0 1.0 52.0
-
4.57
-
-130.1
C
33 a.c
4.75 6.0
4.10-4.70 6.0
4.2-4.8
-
C
I46 n.6
C
146 a
-
4.2-4.7
-
C
146
(continued)
TABLEXXXV (continued) Compound
H-1
H-2
H-3
H-4
H-5
H-6
H-6'
Ji.2
52s
53.4
54.5
55.6
55.6'
56.6'
JFJ
JF,Z
JF.3
JF.4
JF,~
JF,6
JF,~
Methyl 2-deoxy-2-fluoro-~-o-ribo-hexopyranoside 4,6-0- benzylidene-3-deoxy4.10 4.25 1.74/2.3e 2.93 3.05 3.40 7.5 11.3/5.5e 11.5/4.0e 9.0 10.0 4.7 3.5 49.0 11.5a/5.0e 1.5
S References
6F
C
4.09 10.0
The symbol e stands for equatorial, and a for axial. J (H-2e, H-2a) 13.5 Hz." J (H-3a, H-3e) = 11.5 Hz.
138 4.d
=
13.9 Hz. J (H-2e, H-2a)
=
(146) I. Lundt and C. Pedersen, Acta Chem. Scand., 25 (1971) 2749-2756.
TABLEXXXVI
'H-and 'gF-N.m.r. Data for Fluorinated 6-Deoxyhexopyranose Derivatives Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
51.2
52.5
53.4
J4.5
556
Js.6
36,6
JFJ
JF,Z
JF,~
JF,~
JFJ
JF.~
JF,~
2,3,4-Tri-0-acetyl-6-deoxy.cu-~-mannopyranosyl fluoride 5.45
5.00
-
5.32
49.0
3.96 6.0
1.2
6F
S
-119.8
C
150
-208.3
D
147,148
-208.0
D
147,148
-209.9
C
148
-209.9
C
148 *
-197.0
D
149
References
2,6-Dideoxy-2-fluoro-~-galactopyranose a anomer
0.5
49.4
p anomer
13.0
3.5 51.0 14.5 1,3,4-tri-O-acetyl-P6.42 5.39 4.0 10.5 3.5 0.5 49.5 11.5
4.0
4.0 5.33 6.5 3.8
Trifluoromethyl3,4-di-0-acetyl-2,6-dideoxy-cu-~-galactopyranoside 3.9 9.5 3.5 2.0 6.6 0.2 48.5 13.0 3.5 2,6-Dideoxy-2-fluoro-~-glucopyranose a anomer 2.5
50.5
16.0 (continued) 132
TABLEXXXVI (continued)
p anomer -197.2
D
149
C
149
C
149
C
149
0.1 49.5 14.5 1,3,4-tri-O-acetyla anomer
8.0 3.5 4.0 0.5
p
9.5 51.5 anomer
9.5 14.5
9.5
6.5
9.5 49.0
9.5 12.5
9.5
6.5
Trilluoromethyl 3,4-di-O-acetyl-n-~-glucopyranoside 4.0 0.5
9.5 48.0
9.5 12.0
9.5
6.2
b
2,6-Dideoxy-2-fluoro-~-mannopyranose a anomer
20.1 51.0 p anomer
-202.7
D
149
-221.2
D
149
C
149
C
149
30.0
8.0 49.5 30.5 1,3,4-tri-O-acetyl-a7.5
49.0
30.0
Trifluoromethyl3,4-di-O-acetyl-2,6-dideoxy-/3-~-mannopyranoside 0.5 17.0
2.2 50.5
9.8 30.0
8.5 2.0
-220.8 6.2
“ J (OCF,,F) = 1.25 Hz.* J (OCF,,F) = 0.8 HZ.
(147) W. Korytnyk, S. Valentekovic-Honvath, and C. R. Petrie, 111, Tetrahedron, 38 (1982) 2547-2550. (148) C. G. Butchard and P. W. Kent, Tetrahedron, 35 (1979) 2551-2554. (149) G. C. Butchard and P. W. Kent, Tetrahedron, 35 (1979) 2439-2443. (150) Y. V. Voznyi, Bioorg. Khim., 7 (1981) 239-241.
I33
R E N k CSUK AND BRIGITTE I. GLANZER
134
TABLEXXXVII 'H- and lPF-N.m.r. Data for Fluorinated Hex-L(or 3)-enopyranose Derivatives Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
52.3
J3.4
J4.5
J5.6
Js.6,
J6,6
JFJ
JFJ
JFJ
JF,~
JFC
JF,~
JF,~
3-Deoxy-cu-~-erytlrro-hex-2-enopyranosyl fluoride 2,4,6-tn-O-acetyl5.70 5.90 5.40 4.10 4.30 2.0 8.5 56.0 2,4,6-tn-O-benzoyl4.90 6.00 6.25 6.05 4.50 2.0 9.0 56.0 3,4-Dideoxy-~-glycero-hex-3-enopyranosyl fluoride 6-0-acetyl-2-dose a! anomer 5.57 6.29 7.10 4.97 4.40 4.32 10.4 1.7 5.0 5.0 11.8 51.2 5.9 /3 anomer 5.58 6.35 7.18 4.83 4.1-4.6 10.7 3.2 52.0 4.8 6-0-benzoyl-2-dose a! anomer 5.57 6.28 7.12 5.05 4.61 4.55 10.4 1.6 4.8 4.8 12.0 51.0 5.9 p anomer 5.58 6.36 7.13 4.90 4.00-4 S O 10.5 3.0 52.0 4.6 2,3,6-Trideoxy-6-fluoro-cu-~-erythro-hex-2-enopyranoside ethyl 4-0-acetyl5.06 5.85 5.27 4.1-4.40 4.53 2.5 9.6 48.0 48.0 methyl 4-0-acetyl5.00 5.95 5.32 3.75-4.40 4.59 10.2 48.0 48.0 " J (H-I, H-3) H-5) = 2.0 Hz.
=
'
0.7, J (H-3, H-5) = 2.4 Hz. J (H-3, H-5)
=
6F
-141.6
S
References
C
151
C
151
C
151,152 Y
-118.6
C
152 b
-135.2
C
151,152 c
-118.2
C
152
A
153
A
153
2.0 Hz. J (H-1, H-3) = 0.8, J (H-3,
(151) K. Bock and C. Pedersen, Tetrahedron Lerr., (1969) 2983-2986. (152) K. Bock and C. Pedersen, Acra Chem. Scand., 25 (1971) 1021-1030. (153) G. Descotes, J. C. Martin, and Tachi-Dung, Carbohydr. Res., 62 (1978) 61-71.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
135
TABLEXXXVIII 'H- and I9F-N.m.r. Data for Miscellaneous Fluorinated Hexopyranoside Derivatives
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
Ji.2
J2.3
J3,4
54,s
55.6
5 5 , ~
5 6 , ~
JFJ
JFJ
JF.~
JF,~
JFd
JF.6
JF.6'
SF
S
References
Methyl 4-O-benzoyl-6-bromo-2,3,6-trideoxy-2-fluoro-~-~-r~~~-hexopyranoside 4.54 4.45 1.9312.76e 5.02 3.89 3.47 3.60 C 7.5 11.0/5.0 11.0 48.0 Ethyl 4-0-acetyl-2,3,6-trideoxy-6-fluoro-cu-~-e~thro-hexopyranoside 4.4-4.9 1.68-1.85 4.4-4.9 3.3-4.05 4.45 A 48.0 48.0 Ethyl 4-0-benzyl-2,3,6-trideoxy-6-fluoro-cu-~-e~th~o-hex-2-enopyranoside 6.04 5.67 3.30-4.30 4.57 -233.2 2.4 2.4 48.0 48.0
" J (H-30, H-3e) =
138 a
1.53
C
1 I7
11.O Hz.
TABLEXXXIX 'H- and I9F-N.m.r. Data for 2-Deoxy-2-halogenopentopyranosyl Fluorides
Compound H-1 H-2
H-3
H-4
H-5
H-5'
JIJ
J2.3
53.4
54,s
54.5'
JSd*
JFJ
JFJ
JFJ
JF,~
JFS
JF,I'
SF
S
References
C
141
-126.4
C
34
-121.6
C
34
-126.7
C
34
2-Deoxy-~-arabhopyranosylfluoride 2-bromo-P51.2 25.8 3,4-di-O-acetyl-2-bromo-a-
50.5
3.5
3,4-di-O-acetyl-2-iodo-a50.0
5.0
3,4-Di-O-acetyl-2-deoxy-~-lyxopyranosyl fluoride 2-bromoa anomer
50.1
3.5 (continued)
RENB CSUK AND BRIGITTE
136
I. GLANZER
TABLEXXXIX (confinued) Compound H-1 H-2
H-3
H-4
H-5
H-5'
51.2
52.3
J3c
J4.s
54,s
Js,~
JFJ
JFJ
JFJ
JF,~
JF,S
JFF
SF
S
References
p anorner -144.1
34 a
50.8 26.8 2-iodoa anorner -120.4
34
-141.1
34
50.0 3.5 p anomer a
50.8
29.0
3,4-Di-O-acetyl-2-deoxy-~-nbopyranosyl fluoride 2-brornoa anomer 51.3
- 147.6
34
-127.9
34
-141.9
34
- 123.9
34
- 146.5
34
25.1
p anomer
50.4 3.4 2-iodoa anomer 50.7
51.0
27.6
p anorner 6.5
3,4-Di-O-acetyl-2-deox~~-xylopyranosylfluoride
2-bromoa anorner
b
50.3
25.1 p anorner - 128.0
51.0
34
9.0 (continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
137
TABLEXXXIX (continued) Compound H-1 H-2
H-3
H-4
H-5
H-5'
11.2
32.3
53.4
54.5
54,s
J5.5'
JF,l
JF,Z
JFS
JF.4
JFJ
JFJ'
SF
S
References
-138.0
C
34
2-iodo(x anomer b
50.8
29.0 p anomer
C
-122.5 51.1
34
9.2
May have to be reversed with
I Y - D - X Y ~ . I,
May have to be reversed with P-D-~Yxo.
TABLEXL 'H- and I9F-N.m.r. Data for 2-DeoxypentopyranosylFluorides Compound H-1
H-2
H-3
H-4
H-5
H-5'
Ji,2
J2.3
J3,4
54,s
543
J5,S
JFJ
JF,~
JFS
JF,~
JF.S
JF.S
SF
S
References
3,4-Di-0-benzoyl-2-deoxy-~-erythro-pentopyranosyl fluoride a anomer 5.70 2.1-2.6 2.0/3.0a 51.0 p anomer 5.53 1.7-2.4 2.112.1 11.0d6.0e 51.0
5.75 3.0
5.45 10.2
4.45 5.2
3.98 11.2
C
154
5.57 3.0
5.50 2.0
3.70 1.0
3.80 13.0
B
154
4.18 10.6
C
4.05 12.5
C
3,4-Di-O-benzoyl-~-threo-pentopyranosyl fluoride a anomer 5.77 2 . 6 Y 2 . 1 0 ~ 5.75 5.46 4.00 2.6/1.8e 50.7 p anomer 5.77 3.2/3.2e
5.0110.8
9.2
10.0
5.5
5.41
5.22 3.0
4.54
0.6
I54 ax
5.0/36.4 2.2-2.8 3.2e
2.5
154 U.d
51.0
" The symbol a stands for axial, and e for equatorial.
Hz. ,I J (H-20, H-2e)
= 15.0 Hz.
J (H-20, H-2e) = 13.0. J (H-2a, H-2e) = 13.8
(154) K. Bock and C. Pedersen, Acta Chem. Scand., 25 (1971) 2757-2764.
RENk CSUK AND BRIGITTE I. GLANZER
138
TABLEXLI 'H- and 'PF-N.m.r.Data for Fluorinated DeoxypentofuranoseDerivatives Compound H-1 H-2
H-3
H-4
H-5
H-5'
51.1
J2,3
J3,4
54,s
J4.59
Js,r
6F
S
References
JFJ
JF,Z
JFS
JFA
JFJ
JFJ'
-106.5
C
155
-103.2
C
155
-
C
108
-
N
I10
3,5.Di-O-benzoyl-2-bromo-2-deoxy-~-pentof11ranosy1 fluoride a-D-arabino6.07 4.44 0.8 3.0 61.0 7.9 p-D-XY/O-
6.03
4.42
5.66
4.60
4.90
5.85
5.14 4.71 5.8 5.8 65.0 6.0 6.0 2-Deo~y-2-fluoro-cu-D-~rabinofuranosyl bromide 3-0-acetyl-5-0-benzoyl6.45 5.34 5.18 4.60 0.0 12.0 50.0 23.0 3,5-di-0-benzoyl6.67 5.6 5.5 4.75
4.71
5.0
50.0
(155) K. Bock, C. Pedersen, and P. Rasmussen, Acla Chem. Scand., Ser. B , 29 (1975) 185- 190.
TABLEXLII lH- and "F-N.m.r. Data for 3-C-Branched 3-Fluoro-~-glucofuranoses Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
51.2
52.3
J3,4
J4,s
J5,6
J5.6
56,6
JFJ
JF,Z
JFS
JF,~
JF.~
JF,~
JF,~
3-Deoxy-3-fluoro-~-glucofuranose 3-C-(acetoxymethyl)1,2-O-isopropylidene-a5.88 4.63 3.76 4.0
-
4.15
S
References
C
156 Y
11.0
(continued)
I39
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLEXLII (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JLZ
J2.3
53.4
J4.5
J5,6
J5.6
J6.6
JFJ
JF,~
JF.~
JF,~
JF,S
JF.6
JF,~
1.2: 5,6-di-O-isopropylidene-a5.88 4.63 3.70 4.0 11.0 6-0-benzoyl1,2-0-isopropylidene-a5.91 4.64 4.55 3.85 3.8 8.0 10.0 25.0 3-C-(ethoxyallyl)1,2-0-isopropylidene-a6.06 4.82 4.10-4.40
-
4.30
S
References
C
156 b
-
4.32
C
156 c
C
157
3.99
C
157
4.06
C
157
C
157
C
157
C
157
C
157
C
157
3.74-3.92
4.0
11.0
I ,2 :5,6-di-O-isopropylidene-a-
6.03 4.0
4.92 14.5
4.75 8.0 27.0
4.21
-
3-C-[(ethoxycarbonyl)(formylirnino)methyl]-1,2: 5.6-
di-0-isopropylidene-a6.02 4.94 4.0 13.0
4.88 6.0 27.0
4.4 6.0
-
3-C-[ethoxy(ethoxycarbonyl)(formylamino)methyl]-1,2: 5,6di-0-isopropylidene-a5.82 4.67 4.89 2.50 3.82 3.5 6.5 14.5 27.5 3-C-(hydroxymethyl)I ,2: 5,6-di-O-isopropylidene-a5.90 4.67 3.60 4.50 4.0 12.0 1,2-0-isopropylidene-a5.90 4.58 3.60 4.20 4.0 12.0 3-C-[ 1,2-di(hydroxyethyl)l-1,2 :5,6-di-O-isopropylidene-a5.88 4.69 3.80 4.60 4.0 12.0 I ,2-O-isopropylidene-3-C-(methoxyallyl)-a6.07 4.83 4.30-4.67 4.16 4.16 3.5 12.0
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
I40
TABLEXLII (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6’
Jt,t
52.3
53,4
54,s
55.6
55.6’
56,6
JFJ
JF,~
Jp.3
JF.~
JFJ
JF,~
JF,~’
I ,2: 5,6-di-O-isopropylidene-3-C-(methoxycarbonyl)-a5.99 4.68 4.64 4.00 4.40 4.0 8.0 15.0 26.0
S
References
C
157
“ J (H-l’, H-1‘3 = 13, J (H-l’, F) = 14 Hz, J (H-I”, F) = 34 Hz; (H-1‘) = 4.84 p.p.m.; (H-1”) = 4.27 p.p.m. J(H-1’. F) = 13 Hz;J(H-I”, F) = 34 Hz;J(H-I’, H-I”) = 13 Hz; (H-1’) = 4.70p.p.m.; (H-1’7 = 4.24 p.p.m. J (H-l’, H-I”) = 13 Hz; J (H-1’, F) = 14 Hz; J (H-I”, F) = 34 Hz; (H-1’) = 4.84 p.p.m.; (H-1’3 = 4.29 p.p.m. L.
(156) A. J. Brink, 0. G. De Villiers, and A. Jordaan, Carbohydr. Res., 54 (1977)285-291. (157) K.Bischofberger, A. J. Brink, and A. Jordaan, J . Chem. Soc., Perkin Trans. I , (1975)2457-2460. TABLEXLIII ‘H- and I9F-N.m.r. Data for 3-Deoxy-J-C-(monoor di)tluoromethylene-D-hexo(or pento)furanoses
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6’
Jt,2
52.3
53,4
54.5
55.6
55,6’
56,6’
JF,I
JFZ
JF,~
JF,~
JFS
JF.6
JF.6’
SF
S
References
3-Deoxy-3-C-(fluoromethylene)-1,2 :5,6-di-O-isopropylidene-cu-~-hexofuranose ribo-
(2)isomer 5.90 5.06
4.3 1.5
1.4
1.0
( E ) isomer 5.82 5.36 4.0 1.3 0.0 1.3 xylo-
(Z)isomer 5.84 4.93 3.7 0.3 0.3 1.7 (E) isomer 5.81 5.28 3.7 1.0 0.0
1.0
3.36 6.6 1.9
4.00 6.6 0.9
3.76 8.4 0.9
-202.9
4.63 7.6
3.84
-
4.14
-198.5
82.5
5.5
1.8 82.9
4.87 8.3 2.3
4.42 6.0
1.2 82.0
4.67 6.5 1.7
2.1 82.0 2.0
5.12 3.2 1.0
C
37 a
C
37 b
3.78 8.3 1.6
-205.8
0.5
4.00 7.2 0.7
4.42 6.5
4.04 7.1
3.78 8.1
-201.9
0
0
0.5
C
37 c
C
37 d
(continued)
141
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLEXLIII (continued) Compound H-1 H-2 J1.2
J2,3
JF,l
JFJ
H-3
H-4
H-5
H-6
H-6'
J3.4
54,s
554
55.6'
56,6'
JF,~
JFJ
JF,~
JF.~
6F
S
References
3-Deoxy-3-C-(difluoromethylene)-l,2 :5,6-di-0-isopropylidene-cu-o-hexofuranose ribo5.87 4.4 1.4 90.0 xylo5.91 4.0 f0.5 8
5.22 2.6 1.2 5.22
1.0 1 .o
4.86 4.5 3.0 3.0
4.14 6.2 1.0
4.0
3.79 8.0
-247.1 -243.4
C
37
5.5
4.77 7.9 2.8
4.47 6.2 0.5
4.05 7.0 0.2
3.78 8.4 1.7
-244.1 -241.5
C
37
1.o
h
3-Deoxy-3-C-(difluoromethylene)-l,2-0-isopropylidene-(~-o-furanose ribo-hexo5.91 5.28 4.96 3.2 4.3 4.0 1.5 3.2 I 2.8 3.2 erythro-pentodialdo- 1 ,4-furanose 6.04 5.29 5.16 4.1 2.1 '1.0 0.9 3.6 g 2.0 4.0
3.90 2.5 1.2
3.50-3.75 8.5
9.45
-244.4 -241.0
C
158
-245.3 -244.0
C
I58 J
2.1
* (H-3') = 6.83 p.p.rn.; J (H-2, H-4) = 1.4 Hz. (H-3') = 7.01 p,p.rn.; J (H-2, H-4) = 1.3 Hz. (H-3') = 6.82 p.p.m. (H-3') = 6.74 p.p.m. J (H-2, H-4) = 1.2 Hz; J (F, F) = 38 Hz. f Couplings to rrans-oriented fluorine. Y Couplings to cis-oriented fluorine. * J (F, F) = 35.5 Hz. ' J (H-2, H-4)= 1.0 Hz; J (F, F) = 40.8 Hz. J (H-2, H-4) = 1.2 Hz; J (F, F) = 33.8 Hz. J
(158) J. M. J. Tronchet, B. Gentile, J. Ojha-Poncet, G. Moret, D. Schwarzenbach, F. Barbalat-Rey, and J. Tronchet, Carbohydr. Res., 59 (1977) 87-93.
TABLEXLIV 'H- and 'gF-N.m.r. Data for Fluorinated C(or O)-Branched o-Pentopyranose Derivatives Compound H-1 H-2
H-3
H-4
H-5
J1.z
J2,3
J3,4
54.5
54,s'
H-5' Jss,
JF,I
JF,~
JF.~
Jp.4
JF,~
JF,Y
S
1,2-Di-0-acetyl-5-0-benzoyl-2-deoxy-2-fluoro-3-0-formyl-o-arab~ofuranose (Y anomer 6.36 5.71 4.12 4.98 C
References
156
5.5 16.0
(continued)
RENB CSUK AND BRIGITTE I. GLANZER
142
TABLEXLIV (continued) Compound H-1 H-2
H-3
H-4
52.3
53.4
54,5
H-5 54,5'
H-5'
Ji,z
5
References
JFJ
JFJ
JFJ
JF.~
JFJ
JFS,
4.70
C
156
4.70
C
157
4.70
C
156
4.60
C
156
J5.5,
p anomer 6.44
5.35 4.35 3 .O 10.0 21.0 3 4 4Acetoxyrnethyl)-3-deoxy-3-fluoro-~-xylofuranose 5-0-acetyl- 1,2-O-isopropylidene-a5.98 4.64 4.00 4.0 12.0 1.2,5-tri-O-acetyla anomer 6.50 5.46 4.00 5.0
24.0
p anomer
6.10
-
4.10
5.34
14.0
3-Deoxy-3-fluoro-l,2-O-isopropylidene-cu.~-xylofuranose 3-C-(hydroxymethyl)5.92 4.58 4.0 12.0 3-C-(ethoxyallyl)5.95 4.68 4.0 12.0
3.60
-
4.40
C
157
4.30
-
3.81
C
157
5.0
TABLEXLV 'H- and I9F-N.m.r. Data for Miscellaneous, Fluorinated Branched Monosaccharides Compound H-1 H-2
H-3
H-4
H-5
&,a
J3.4
J4.5
J5.6
H-6 55,~
H-6'
JI,~ JF.1
JFJ
JF,~
JF,~
JFS
Jp.6
JF,~'
6F
S
References
56,6'
5(R)-5-C-Acetoxy-6-deoxy-6-fluoro-l,2 :3,4-di-O-isopropylidene-~-~-arabino-hexo-l,5pyranosd-dose 5.55 4.13 0.0 3.9
4.52l' 6.2
4.62"
4.69 46.0
5.13 9.6 46.8
-236.0
C
48
(continued)
N .M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
143
TABLEXLV (continued) ~~______
Compound H-1 H-2 J1t
4
3
JF,l
JF.2
H-3
H-4
H-5
H-6
H-6'
J3.4
J4.5
55.6
55.6'
56.6'
JFS
JF,~
JF.5
JF.6
JF.6'
SF
S
References
~~~
l-O-Acetyl-2,3,5,64etra-O-benzoyl-4-deoxy-4-fluoro-~~-hexofuranose galacto6.56 5.82 6.11 C 159 2.2 4.7 0.0 15.2 4.0 gluco6.69 5.47 5.88 6.10 5.02 4.72 C 159 0.0 0.0 0.0 0.0 7.3 5(S)-5-C-Acetoxy-3,5-O-benzylidene-6-deoxy~0uoro-l,2-O-isopr~pylidenea-D-xylo-hexo1,4-furanosd-dose 6.02 4.66 4.23" 4.62" 4.90 5.13 -240.2 C 48 3.4 0.0 0.0 9.7 45.1 46.7 2,~,4-Tri-~-acetyl-2-fluoro-~-~-ribopyranosyl fluoride 6.47 5.31-5.61 4.22 3.83 -153.0 C 98 2.0 1.5 13.0 -133.0 51.0 0.0 1.5 Trifluorometbyl 2,3,4-tri-0-acetyl-2-fluoro-/3-~-ribopyranos~de 6.44 5.58 5.44 4.26 3.86 -133.0 C 98 4.0 2.5 2.5 13.5 6.5 1.2 1-0-Acetyl-2,3,5-trii-O-benzoyl-4-fluoropentofuranose a-L-lyxo-
6.66 3.0 0.0
5.91 5.1 0.8
6.19
4.85
4.65
C
159
17.3
P-D-ribo-
6.61 5.78 6.00 4.78 5.53 C 159 0.0 5.3 8.0 1.0 3.9 4-0-Acetyl-5-deoxy-5-fluoro-1,2-O-isopropylidene-3-O-tosyl-~-~-~~reo-pento-l,4-furanos-4dose 6.08 4.83 5.28 4.48 4.73 -236.1 C 48 3.8 45.7 46.4 a
The assignments may have to be reversed.
(159) R. J. Ferrier and S. R. Haines, J . Chem. SOC.,Perkin Trans. 1 , (1984) 1675-1681.
RENk CSUK AND BRIGITTE I. GLANZER
I44
TABLEXLVI lH- and lgF-N.m.r. Data for Fluorinated Ketopyranose Derivatives Compound H-1 H-1' J3,4 J1.r JF,I
JF,V
H-3
H-4
J4,s
55.6
H-5 55.6
56.6'
H-6
JFJ
JF.~
J F ~
JF,~
H-6'
6F
S
References
C
160
D
161
C
162
JF,~'
l-Deoxy-l-fluoro-2,3 :4,5-di-O-isopropylidene-~-fructopyranose 4.37 4.37 4.25 4.64 4.39 3.74 3.92 -230.1 10.0 8.0 3.0 2.0 12.0 48.0 48.0 1.5 4-Deoxy-4-fluoro-~~-fructopyranose 3.72 3.56 4.06 4.78 4.26 4.03 3.75 11.8 9.75 3.5 1.6 2.0 13.0 1.8 12.9 49.0 6.5 1.3 7.8 4-Deoxy-4-fluoro-1,2-O-~sopropylidene-~-~-sorbopyranose -195.6 5.0 3.0 9.0 46.0 9.0
(160) P. J. Card and W. D. Hitz, J . Am. Chem. Soc., 106 (1984) 53484350. (161) M. BudMnsk$, M. Cern$, J. Dole2alovB, M. Kulhhnek, J. Pacak, and M. Tadra, Collect. Czech, Chem. Commun., 49 (1984) 267-274. (162) M. Sarel-Imber and E. D. Bergmann, Carbohydr. Res., 27 (1973) 73-77.
TABLEXLVII 'H- and '9F-N.m.r. Data for Mono- and Di-fluorinated Ketofuranose Derivatives Compound H-1 H-1'
H-3
H-4
H-5
H-6
54.5
55,6
Js,~
56.6
H-6'
JIJ*
53.4
'JFJ
JFJ
JF,3
JF.4
JF,S
JF,6
JF,~
"JFJ
JFJ-
JFJ
JF,~
JF.5
JF,6
JF,~
SF
S
References
1,3,4,6-Tetra-O-ace~l-~-fructofuranosyl fluoride a anomer 4.2-4.5 1.0
p anomer 4.2-4.5 7.0
5.55 5.0 7.0
5.00
5.4-5.7
A.2-4.5-
C
163
d.2-4.5-
C
163
16.0 6-O-Benzoyl-l-deoxy-l-flnoro-2,3-O-isopropylidene-~-~-f~ctofuranose 4.38-4.6 1 -225.2 C
164 b
47.7 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
145
TABLEXLVII (continued)
Methyl 3,4,6-tri-O-benzoyl-l-deoxy-l-fluoro-~-fructofuranoside a anomer 4.68 4.39 5.81 5.60 4 . 4 1 - 4 . 1 7 -230.8 B 164,165 b 2.2 4.9 46.9 p anomer 4.68 4.39 5.81 6.12 -232.3 C-B 164, 6.5 5.5 165” 46.9 6-Deoxy-6-fluoro-2,3-O-isopropylidene-l-O-~tolylsu~onyl-~-~-f~ctofuranose 164,” 4.05-4.95 -226.8 C 18.1
46.2
1,6-Dideoxy-l,6-di~uoro-2,3-O-isopropylidene-~-~-fructofuranose 4.52
4.57
5.0
47.1
5.0 17.7
C
164, 166,”
-233.1 -230.3
C
164, 165,”
-230.9 -234.8
C-B
164, 165,”
-225.0 -225.5
46.4
Methyl 3,4-di-0-acetyl-1,6-dideoxy-1,6-d~uoro-~-fructofuranoside a anomer 4.31
4.31 2.2
5.61 6.4
5.19 3.5
3.94 3.5
4.36
46.4 22.0
p anomer 4.42 9.6 46.6
4.26 1.3
5.19 7.1
5.64 5.0
3.90 2.4 22.3
41.3 4.2-4.34 10.5 46.9
“ The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. 6F values were taken from Refs. 164 and 165; although no standard was reported, C6F6 had obviously been used. (163) B. Erbing and B. Lindberg, Acta Chem. Scand., Ser. B , 30 (1976) 12-14. (164) R. D. Guthrie, I. D. Jenkins, and R. Yamasaki, Ausf.J . Chem., 35 (1982) 1003-1018. (165) R. D. Guthrie, I. D. Jenkins, and R. Yamasaki, Ausf.J . Chem., 35 (1982) 1019-1029. (166) J. Pacirk, J. HalaSkovir, V. Stepirn, and M. Cvernq, Collecf. Czech. Chem. Commun.,37 (1972) 3646-3651.
RENh CSUK AND BRIGITTE I. GLANZER
I46
TABLEXLVIII 'H- and "F-N.m.r. Data for 2-Deoxy-2-fluorohexopyranosylFluorides Compound H-1 H-2
&'I
H-3
H-4
H-5
H-6
H-6'
J1.t
Ja.3
53.4
54.5
55.6
J5,6'
J6.6'
YF.1
JFJ JFZ
JF,~ JF,~
JF,~
JF,~
JF,~ JF.~
J F , ~ J(F,F)
JF,~ J F ~
'JF,~
m
S
a
References
JF,~
2-Deoxy-2-fluoro-D-gdactopyranosy~ fluoride a anomer 54.3
24.5 48.9 14.6 3,4,6-tri-O-acetyla anomer 5.76 4.68 5.34 2.7 9.7 3.2 52.5 23.0 0.9 48.0 11.0 p anomer
4.9 5.48
4. 5
4. 5
4.06
1.0
3.5
52.5 14.3 5.0 51.3 14.8 2.5 2-Deoxy-2-fluoro-~-glucopyranosylfluoride (Y anomer 54.1 23.8 0.0 47.7 13.8 3,4,6-tri-O-acetyla anomer 5.80 4.54 5.54 2.9 9.6 9.5 53.3 23.8 0.5 0.0 48.3 12.3 p anomer 5.41 4.46 5.32 6.1 7.9 8.9 51.7 11.2 1.0 4.0 49.0 15.0
5.10 9.5 0.0 5.10 9.0
4.06
0.0
0.0 0.0
3.11 9.9
2.95 2.4
D
-153.0 c-212.0 18.0
C
-142.3 -209.4 14.5
C
147
-150.1 -204.0 20.8
D
47,147, 167
47,147
4
,46,53, 54.147
-
4.42
-151.5 -204.5 18.8
C
18.36, 58,147, 168,169
4.26
4.20 12.0
-140.3 -200.9 15.8
C
18,36, 147
3.36 5.9
3.21 12.4
-147.5 -222.4 12.7
D
47,167, 170
0.0 0.0
3.89
-152.2 -211.9 19.6
2-Deoxy-2-fluoro-~-mannopyranosyl fluoride
p anomer
5.01
0.0 47.4 17.8
4.41 2.7 2.8d 51.8
3.23 9.7 30.0
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
147
TABLEXLVIII (continued)
3,4,6-tn-O-acetyla anomer 5.76 4.89 5.27 5.42 4.42 4.06 9.0 10.0 2.0 2.5 48.0 0.0 2.5 0.0 0.0 0.0 4.0 48.5 27.0 p anomer 5.51 4.90 5.14 5.29 3.86 4.30 4.30 1.0 2.5 8.5 7.5 7.0 48.5 8.0 0.5 0.8 13.5 '49.0 22.4 2.0 0.5 3,4,6-Tri-0-acetyl-2-deoxy-2-fluoro-~-~-talopyranosyl fluoride 4.28-3.90 5.33 4.69 5.07 5.19 1.0 3.0 3.0 1.0 48.0 6.0 51.0 25.0 14.5
-143.4 -207.2 20.0
C
18,36
-146.4
C
18,36, 58,147, 168,I69
C
45,147
I- 277.0
13.5 -145.8 -218.4 12.8
The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Ref. 53 reported a coupling of 20 Hz. Ref. 54 reported a chemical shift of -223 p.p.m. Ref. 47 reported a coupling of 9.8 Hz; additional couplings: J (F, H-4) = 1 Hz, and J (F, H-6) = 1 Hz. 'Ref. 169 reported a coupling constant of 34 Hz. 'Ref. 147 reported a chemical shift of -220.1 p.p.m. (I
(167) N. Satyamurthy, G. T. Bida, H. C. Padgett, and J. R. Barrio, J . Carbohydr. Chem., 4 (1985) 489-512. (168) J. Adamson, A. B. Foster, L. D. Hall, and R. H. Hesse, Chem. Commun., (1969) 309-310. (169) T . Ido, C. N. Wan, J. S. Fowler, and A. P. Wolf, J . Org. Chem., 42 (1977) 23412342. (170) S. G. Withers, I. P. Street, and S. J. Rettig, Can. J . Chem., 64 (1986) 232-236.
TABLE XLIX IH- and '9F-N.m.r. Data for 3(or 4, or 6)-Deoxy-3(or4, or 6)-fluorohexopyranosyI Fluorides
3-Deoxy-3-fluoro-~-glucopyranosylfluoride 2,4,6-tri-O-acetyla anomer 5.73 5.02 4.79 5.29 4.07 4.26 4.14 2.6 9.5 9.5 9.5 12.5 52.2 22.6 1.0 0.5 51.5 13.5 1.0 4.0 14.5 p anomer 4.57 5.31 3.79 4.24 4.21 5.27 5.2 12.4 6.0 7.7 8.5 9.5 51.5 10.8 0.0 0.0 0.0 15.0 51.3 13.5 1.0 2,3,6-Tri-0-acetyl-4-deoxy~4-fluoro-~-galactopyranosy~ fluoride a anomer 2.3
9.9 24.0 2.8 R anomer
2.5 25.4
0.5
-149.8 -201.1
C
II
-138.8 -196.0 3.0
C
11
C
19
C
19
1 .o
3.7 28.0
1.0
10.5 2.5 1.0 9.6 2.5 0.8 1.3 25.6 25.2 1.0 4-Deoxy-4-fluoro-~-glucopyranosyl fluoride 2,3,6-tri-O-acetyla! anomer 5.68 4.87 5.6 4.52 4.5 2.8 10.2 8.9 9.5 52.0 23.7 3.0 0.8 14.6 48.5 p anomer 5.37 5.02 5.30 4.65 3.96 4.48 5.8 7.4 8.6 9.4 2.9 4.9 50.7 10.2 0.8 0.8 0.9 0.6 0.5 0.0 15.8 49.5 4.9 1.6 6-Deoxy-6-fluoro-~-glucopyranosyl fluoride 2,3,4-tri-O-acetyla anomer 5.75 4.94 5.50 5.17 4.03 4.51 2.7 9.9 9.4 10.0 2.2 3.5 52.4 23.8 23.9 47.0
1.0
6.7
1.3 1.0
4.12
-150.0 - 199.5 0.6
C
12
4.24 12.1 0.6 1.9
-137.0 -199.4 3.1
C
12
4.45 10.8
-150.4 -234.8 0.2
C
84
47.0
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
149
TABLEXLIX (continued)
p anomer 5.4
4.93
-
5.5
52.7
5.25 9.0
3.95
4.51
4.51
10.4 20.6
46.6
-137.0 -232.2 0.9
C
84
46.6
" The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom.
TABLEL 'H- and I9F-N.m.r. Data for Dideoxydifluorohexo-pyranosesand -pyranosides Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
Jz.3
J3,4
54.5
Js,6
55.6'
56.6'
'JFJ
JFJ
JF.~
JF,~
JFJ
JF.6
JF,~
'JF,I
JFJ
JF.3
JF,4
JF,~
JF,6
JF,~
6F1 6F2 J(F,F)
S
-118.8 - 124.3 246.0
s
171
-119.9 -141.4 241 .O
s
171
-192.5 -196.3
A
65,77
-215.0 -234.2
A
'
References
2-Deoxy-2,2-difluoro-~-urubino-hexopyranose (Y
anomer
6.0 p anomer
17.0
6.0 23.0
6.0 20.5
3,6-Dideoxy-3,6-difluoro-~~-allopyranoside methyl 4.50 3.41 8.0 1.3 29.3
4.91 53.7
3.64 10.0 29.3
3.78 4.5 25.6
methyl 2,4-di-O-benzoyl5.08 5.20 5.50 5.33 10.5 8.0 2.0 2.0 1.5 28.0 54.0 27.0
4.44 4.0 24.5
4.61 2.0 47.6 4.73 2.0 47.5
4.64 11.0
b
47.6 4.76 10.5
65
47.5 (continued)
RENE CSUK AND BRIGITTE I. GLANZER
I50
p-nitrophenyl 5.46 3.86 5.01
8.0
28.0
52.0
3.89
10.0
4.15 4.0
5.04
8.5
28.0
52.0
4.14 10.0
29.0 28.0
phenyl 5.21
4.61 4.0
4.0
48.0 4.61 2.0
65
-211.1 -234.5
65
48.0 4.12 10.0
28.0
25.0 46.0 4,6-Dideoxy-4,6-difluoro-~-galactopyranoside methyl a anomer '4.17 4.82 4.0 2.6 0.0 30.6 50.3 30.6 13.5 46.6 p anomer
-211.9 -235.5
46.0
-219.1 -229.9
172
- 196.2
71
-219.9 -230.1
65
-216.9 -231.9
27,ll
- 196.9
65
77
3
46.6 -206.2
30.5 phenyl a5.63 4.0 3.5 10.0
4.2 29.0
51.3 4.96 51.0
30.5 13.4
46.7
4.34 1.2
4.55 4.6 43.0
Methyl 4,6-dideoxy-4,6-difluoro-~-tdopyranoside a anomer
4.88 3.5
3.19
3.83
32.0
4.19
48.6
4.01
32.0 13.8
4.62
2.0 46.6
46.1 4.68 9.5 46.0 4.62 2.0 46.6
2,3-O-isopropylidene-a-
-235.1
25.0
52.0
25.0 25.0
6-Deoxy-6,6-difluorogalsetopyranose 1,2,3,4-tetra-O-acetyl-ta anomer
6.39 3.1
5.25
10.7
5.39 3.3
5.65
4.58 5.9
48.0
6.02 55.5
d
48.0
6.02
173
54.4 (continued)
I5 I
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLEL (continued)
p anomer
5.76 8.5
5.36 10.7
5.10
5.60
3.3
4.00 5.5
I ,2:3,4-di-O-isopropylidene-a-~-
5.56 4.9 1.8
4.36
4.65 7.7 1.3
4.36
3.90 6.6
5.78 55.4 -
5.78
5.5
I73
C
173, 174
54.4 5.84 57.5 54.0
10.0
C
-131.6 -133.6 298.2
a The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Ref. 65 reported chemical shifts of -217.6 and -234.6 p.p.m., respectively. Ref. 172 reported for H-1 = 4.88 p.p.m. Ref. 77 reported chemical shifts of -196.7 and -199.6 p.p.m., respectively. ' Ref. 174 reported data for the corresponding D enantiomer.
(171) J. Adamson, A. B. Foster, and J. H. Westwood, Curbohydr. Res., 18 (1971)345-347. (172) C. W.Somawardhana and E. G. Brunngraber, Carbohydr. Res., 94(1981)cl4-cl5. (173) J. A. May, Jr., and A. C. Sartorelli, J . Med. Chem., 22 (1979)971-976. (174) M.Sharma, I. Kavai, Y.L. Fu, and M. Bobek, Tetrahedron Lett., (1977)3433-3436. TABLELI IH- and I9F-N.m.r.Data for Difluorinated Anhydrohexo-pyranose and -furanose Derivatives Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
6F1
S
31.2
Jz.3
J3,4
54.5
55.6
J6.6'
6F.2
a
VF.1
JFJ
JFJ
Jp.4
JF,S
Js,~ JF,~
JF.~'
'JFJ
JF,Z
JF,~
JF.~
JF,~
JF.~
JF,~
J(F,F)
3-O-Acetyl-1,6-anhydro-2,4-dideoxy-2,4-difluoro-~-~-glucopyranose
5.57
4.38
5.13
4.23
4.78
C
17.5 17.5 45.0 1,6-Anhydro-2,4-dideoxy-2,4-difluoro-~-~-ribo-hexo-pyranos-3-ulose hydrate 5.49 4.07 4.23 4.73 4.03 3.75 S 2.2 2.I 1.2 5.9 7.2 2.2 48.0 1.0 4.0 9.6 9.6 2,5-Anhydro-l-deoxy-l,l-d~uoro-~-hexitol
References
118
45.0
arabinoa anomer
5.99 3.0
D
I75 h
176 (continued)
152
RENE CSUK AND BRIGITTE I. GLANZER TABLELI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JIS
523
53.4
54,s
55.6
53.6
J6.6'
6F1 6F2
'JPJ
JFJ
JFS
JF,4
JFJ
JF,~
Jp.6,
J(F,F)
'JFJ
JFJ
JFJ
JF,~
JF,S
JF,~
&,6*
55.1 3,4,6-tri-O-acetyI5.86 3.6 55.0 ribo5.60 5.40 4.0 54.0 12.0 12.0
-128.2
5.40
4.0
4.0
3,CAnhydro-6,6-di!luoro-~-glucofurnnose 1,2-O-benzylidene-a6.11 4.85 4.92-5.01 4.44 -82.9 3.6 4.0 -76.5 11.0 144.0 7.0 1,2-O-isopropylidene-u5.92 4.70 4.78-4.86 4.39 -82.8 3.6 4.0 -76.4 11.0 144.3 7.0 3,6-Anhydro-6,6-difluoro-l,2-O-isopropylidene-~~-idofuranose 5.92 4.76 4.69 4.95 4.24 -87.0 3.6 0.7 3.5 0.6 -68.7 0.4 3.5 5.8 3.2 150.4 1.2 0.6
S
References
a
C
176
C
177
C
125
C
125
C
125
The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. J (H-2, H-4) = 1.3 Hz. J (H-I, H-4) = 0.6 Hz; J(H-2, H-4) = 0.6 H z ; J (H-2, H-5) = 0.6 Hz; and J (H-3, H-5) = 0.6 Hz.
(175) J. PacBk, M. BraunovB, D. StropovB, and M. Cerng, Collecr. Czech. Chem. Commun., 42 (1977) 120-131. (176) K. R. Wood and P. W. Kent, J . Chem. SOC., C, (1967) 2422-2425. (177) P. W. Kent and J. E. G. Barnett, Tetrahedron, Suppl., 7 (1966) 69-74.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
I53
TABLELII 'H- and I9F-N.m.r.Data for 2,6-Dideoxy-2-fluorohexopyranosylFluorides Compound
H-1
H-2
H-3
H-4
H-5
H-6
H-6'
11.2
J2J
J3.4
54.5
J5,6
J5,v
J6,@
%,I
JFJ
JF,~
JF,~
JFJ
JF,~
JF,~
*JFJ
JF,~
JF,3
JP.4
JFJ
Jv.6
JF,~'
m1
m
S
References
0
J(F,F)
2,6-Dideoxy-2-fluoro-~-galactopyranosyl fluoride (Y
anomer
54.4 24.5 0.6 48.2 13.4 3,4-di-O-acetyl(Y anomer 3.0 53.5 0.5
9.5 23.2 48.8 13 anomer
-151.6 -212.2 19.5
D
147
-152.1 -211.9 18.3
C
147, 148b
-142.7 -210.4 15.4
C
147
C
149
C
149
4.2
3.5
2.0
11.3
3.8
6.4
52.8 14.5 4.9 51.5 13.3 2.9 3,4-Di-0-acetyl-2,6-dideoxy-2-luoro-a-~-glucopyranosyl fluoride 3.2 53.5 0.2
9.8 24.0 48.0
9.8
9.8
6.2
19.0
12.5
3,4-Di-0-acetyl-2,6-dideoxy-2-fluoro-~-~-mannopyranosyl fluoride 0.5 48.5 17.0
2.3 4.2 52.0
9.5
7.5
6.2
-148.3 -221.6 13.0
28.0
" The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Ref. 148 reported a chemical shift of -148.1 p.p.m. for F-I.
154
RENE CSUK AND BRIGITTE I. GLANZER
TABLELIII
‘Hand l9F-N.m.r.Data for Difluorinated Hex-5-enofuranoses
5,6-Dideoxy-1,2-0-isopropylidenehex-5-enofuranose 6-chloro-5,6-difluoro-3-O-methyl-a-~-xy/o(Z) isomer 5.89 4.62 3.67 4.98 5.47 -91.1 C 178 3.8 3.2 9.0 2.0 9.9 (E) isomer 5.73 4.46 3.56 4.85 5.12 -87.3 T 178 3.9 2.9 8.8 2.9 27.8 6,6-difluoro-3-O-methyl-~-~-/yxo4.91 4.98 -79.0 C I79 10.2 -74.0 b 0.3 2.3 35.3 e 0.8 25.2 6,6-difluoro-3-O-methyl-a-~-ribo4.64 4.34 -80.2 c 179 9.8 -76.8 b I .3 1.5 30.9 0.9 23.7 6,6-difluoro-3-O-methyl-a-~-xy/oC 179 -79.6 4.90 4.58 -77.5 9.5 33.5 1.7/1.1 1.6/25.0 3,5,6-Trideoxy-6,6-difluoro-1,2-O-isopropylidene-~-~-erythro-hex-5-enofuranose 5.82 4.74 1.61/2.23 4.84 4.32 -77.0 C 178 d.e. 3.7 4.6 10.7l4.5 9.1 -77.9 b 0.8 2.5 34.8 c 1.0 2.4 1,2-~-lsopropylidene-5,6-dideoxy-6,6-difluoro-cu.~-xy~o-hex-5-enofuranose 3-0-benzyl 4.9 4.67 -89.6 C I79 9.8 -87.9 b 2.0 2.0 33.4 c 2.2 23.4 3-O-methylC 179 4.90 4.58 -79.6 9.5 -77.5 b I .7 1.6 33.5 1.1
25.0 (continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
155
TABLELIII (continued)
3-O-benzyl-a-
4.91
4.67 -89.6 C 179 -87.9 9.8 d 2.0 2.0 33.4 2.2 23.4 Methyl 5,6-dideoxy-6,6-difluoro-2,3-O-isopropylidene-~-~-r~~o-hex-5-enofuranoside 4.97 4.64 4.64 4.90 4.46 -74.2 C 178 10.4 -76.1 1.2 2.8 34.0 1.2 24.0 The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Coupling to cis-oriented fluorine atom. Coupling to trans-oriented fluorine atom. J (H3, H-3') = 13.5. e Ref. 178 reported further examples for higher sugars.
(178) J. M. J. Tronchet and A. P. Bonenfant, Helu. Chirn. Acta, 63 (1980) 1644-1653. (179) J. M. J. Tronchet, A. P. Bonenfant, and F. Barbalat-Rey, Carbohydr. Res. 67 (1978) 564-573.
TABLELIV 'H- and I9F-N.rn.r.Data for Difluorinated Pentoses ~~
Compound H-1 H-2
H-3
H-4
H-5
H-5'
JI,~
52.3
J3.4
54.5
J4.5~
JS,Y
'JF,~
JFJ
JFJ
JF,~
JF,S
JF,V
'JF.1
JF3
JFJ
JF.4
JF,~
JF,Y
sF1
m
J(FJ9
3,4-D~-O-acetyl-2-deoxy.~-fluoro-~-~-arabinopyranosyl fluoride 5.86 4.31 5.50 4.16 3.85 -156.0 3.0 1.5 2.0 13.5 -210.0 53.0 0.5 2.0 2-Deoxy-2-fluoro-D-lyxopyranosy~ fluoride p anorner 3.0 53.0 4.5
3.0 22.0 45.5
3.5
2.5
S
References
C
53,54, 98
D
99
a
12.2
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
I56
TABLELIV (continued) Compound H-1 H-2
H-3
H-4
H-5
JIJ
JZJ
J3.4
J4.5
54,s’
H-5’
%,I
JF,Z
JFJ
JF,~
JF.S
JFJ’
‘JFJ
JFJ
JF.~
JF,~
JF,S
JFJ~
3,4-di-O-acetyla anomer
p anomer 3.6 53.0
3.6 47.0
2.0
12.5
25.0 4.0
3,4-D~-O-acetyl-2-deoxy-2-fluoro-~-~-~bopyranosyl fluoride 5.7Sb 4.9Ib 4.0b 3.67 3.5 10.0 5.0 10.0 24.5 44.0 3,4-Di-O-acetyl-2-deoxy-2-fluoro-~-~-xylopyranosyl fluoride
5.60 3.5 53.5
2,4-Di-O-acetyl-3-deoxy-3-luoro-/3-~-xylopyranosyl fluoride
sF1
m
J(F,F)
S
a
References
-156.0 -215.0
C
54
-156.0 -215.0 19.0
C
533
-151.0 -206.0
C
98
-152.0 -212.0
C
5334
5.41 5.0 4.65 5.0 4.31 3.72 c 11 -137.7 2.7 4.7 4.7 3.0 3.5 12.8 -195.7 0.5 0.0 49.8 7.7 0.2 10.4 0.0 12.5 45.5 12.5 2.5 0.3 3,5-Dideoxy-3,5-d~uoro-l,2-O-isopropylidene-cu-~-xylofuranose 5.9 5.30 -209.8 T 2033, 4.0 -231.5 I80 1.2 11.0 49.5 29.9 1.4 11.9 46.0 Methyl 5-deoxy-5,5-difluoro-~-ribofuranoside 2,3-O-isopropylidene-PC 181 -129.0 - 129.0 Methyl 2-deoxy-2,2-difluoro-3,4-O-isopropylidene-~~-e~~~r~-pentopyranoside -126.2 C 181 - 146.1 Methyl 4-deoxy-4,4-di8uoro-2,3-O-isopropylidene-/3-~-e~~~r~-pentopyranoside C 181 -113.1 - 115.9 256.5 The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. The assignments may have to be reversed. J (H-1, H-3)= 0.5 and J (H-3, H-5’) = 0.8 Hz.
(180) A. B. Foster and R. Hems, Carbohydr. Res., 10 (1969) 168-171. (181) R. A. Sharma, I. Kavai, Y. L. Fu, and M. Bobek, Tetrahedron Lett., (1977) 34333436.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
157
TABLELV 'H- and IgF-N.m.r. Data for Difluorinated Amino Suears Compound
H-l
H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
JZ.3
J3.4
54,s
554
55.6'
5 6 , ~
'JFJ
JF,Z
JFJ
JF,4
JFJ
JF.6
JF,~
*JFJ
JFJ
JFJ
Jp.4
JFJ
JF,~
JF,~
sF1
m
S
a
References
J(F,F)
Methyl 2-acetam~do-2,4,6-trideoxy-4,6-difluoro-~-~-g~actopyranos~de -225.0 P -236.7 33.8 63.0 33.8 13.5 47.3 47.3 3-0-acetyl-222.9 C -227.7 28.1 54.0 28.1 13.5 45.0 45.0 Methyl 2-acetamido-3-O-acetyl-2,4,6-tdeoxy-4,6-difluoro-~-~-glucopyranoside 3.33 -200.4 11.0 8.7 -240.8 13.5 48.4 2.8 24.8 47.3 47.3 Methyl 2-benzamido-2,4,6-tdeoxy-4,6-d~uoro-~-~-g~a~opyranoside 3-0-acetyl-223.4 -237.8 25.9 54.0 25.9 12.4 47.3 47.3 3-0-benzyl-224.0 -236.5 26.4 55.1 26.4 16.9 48.9 48.9 Methyl 2-benzamido-2,4,6-tdeoxy-4,6-difluoro-t~-glucopyranoside 3-0-acetyl5.49 -200.3 10.6 8.7 -240.8 15.8 48.4 1.1 25.9 47.3 47.3 3-0-benzyl-198.1 -240.1
134
134
134 b
134
134
134 b
134
The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Partial listing of coupling constants in A is given, too.
RENE CSUK AND BRIGITTE I. GLANZER
158
TABLELVI ‘H-and I9F-N.m.r. Data for Tri- and Tetra-fluorinated Monosaccharides
3,6-Anhydro-5-deoxy.5,6,6-trifluoro-1,2-0-isopropylidene-~-~-glucofuranose 6.00 4.78 4.94 5.07 5.35 -216.8 C 125 b 3.5 0.6 3.4 4.5 -79.3 3.5 6.3 2.0 48.0 -75.7 1.3 1.5 9.0 0.6 5.6 3,6-Anhydro-5-deox~5,6,6-triluoro-1,2-0-isopropylidene-~-~-idofuranose 5.91 4.78 5.07 4.95 5.10 -201.1 c 125 3.6 0.6 3.7 0.6 -86.6 5.6 9.4 47.4 -68.5 0.6 3.6 2.8 0.6 1.4 3,4,6-Trideoxy-3,4,6-trifluoro-c~-~-galactopyranosyI fluoride 5.84 4.21 4.94 5.27 4.57 4.80 4.73 -154.3 M 182 10.1 2.7 5.2 6.5 9.5 -221.3 d 5.4 53.0 25.0 -207.1 2.9 11.0 47.2 -232.5 26.8 51.4 28.1 14.2 47.0 47.0
“ The symbols I, m, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atoms. J (H-I, H-3) = 0.6; J (H-1, H-5) = 0.4; J (H-2, H-4) = 0.6; J (F-5, F-6) = 12.2; J (F-5, FA’)= 12.2; J (F-6, F-6’) = 140.4 Hz. J (H-1, H-3) = 0.6; J (H-2, H-4) = 0.6; J (H-2, H-5) = 0.6; J (F-5, F-6) = 12.2; J (F-6, F-6’) = 152.6 Hz. d J (F-I, F-3) = 3.7; J (F-3, F-4) = 13.7 Hz. (182) G . H.Klemm,R. J. Kaufman,and R. S . Sidhu,Tetrahedron Lett., (1982)29272930.
TABLELVII IH-and 19F-N.m.r.Data for Acyclic Monosaccharides 2,2’-O-Methylenebis(I-deoxy-l-fluoro-~-glycerol) (C, Ref. 183) H-l = H-I’ = 4.58p.p.m.; J (H-I, H-2) = 5 Hz; J (F, H-I) = J (F, H-1‘) = 45 Hz 2,2‘-O-Methylenebis(3-O-benzoyl-I-deoxy-l-fluoro-~-glycerol) (C, Ref. 183) H-1 = H-I’ = 4.63p.p.m.; J (H-I, H-2)= 4.5 Hz; J (F, H-I) = J (F, H-1’) = 47.5Hz 1,6-Dideoxy-l,6-difluorogalactitol (D,Ref. 184) = J (H-l’, F) = 50 Hz; J (H-2, F) = 18 Hz;6F = -227.6 p.p.m.
J (H-I, F)
(continued)
N.M.R.SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
159
TABLELVII (continued)
Ref. 184) 24 Hz;6F = -232.5 p.p.m.
1,6-Dideoxy-l,6-difluoro-2,3 : 4,6-di-O-isopropylidenegalactitol (s,
J (H-I, F) = J (H-l', F) = 49 Hz;J (H-2, F)
=
I ,2,4,5,6-Penta-O-acetyl-3-deoxy-3-fluoro-~-mannitol (Ref.73) in C in B [J (H,F)1 [J (H,F)1 H-l = 4.55(2.6) J(1,l') 4.63(2.6) H-I'= 4.13(2.2) 3.97(2.I ) J( 12) H-2 = 5.11 (6.8) 5.32(6.8) J( I ' 2) H-3 = 4.85(45.6) 4.87(46.0) J(2,3) H-4 = 5.66(30.I ) J(3,4) H-5 = 5.31 (0.0) 5.50 (1.0) J(43 H-6 = 4.38(0.0) 4.48(0.0) J(5,6) H-6' = 4.16(0.0) 4.17(0.0) J(5,6') J(6,6')
in C
in B
12.5 2.5 4.3 9.3 1.6 7.1 2.6 5.7 12.5
12.4 2.6 4.8 9.3 1.7 7.2 2.7 5.4 12.6
3,4-O-Benzylidene-l,6-dideoxy-l,6-difluoro-2,5-O-methylene-~-mannitol (C, Ref. 183) H-l = H-I'= H-6= H-6'= 4.71 p.p.m.; J (H-I, F) = J (H-l', F) = 47.5Hz. 1,6-D~deoxy-1,6-difluoro-2,5-O-methylene-~-mannito~ (A,Ref. 183) H-l= H-I'= H-6= H-6'= 4.66p.p.m.; J (H-I, F) = J (H-l', F) = 47.5Hz. 3-Deoxy-l-fluoro-3-iodo-l,2 :5,6-di-O-isopropylidene-a-~-xy/o-4-hexulose (B, Ref. 185) H-l= 6.13;H-2= 4.84;H-3= 4.64p.p.m.;J (H-I, H-2)= I : O Hz;J (H-2, H-3)= 10 Hz;J (F, H-I)= 66 Hz;J (F, H-2)= 15 HZ
1,2-Dideoxy-l, I-difluoro-3,4 : 5,6-di-O-isopropylidene-~-arabino-hex-I-enitol (C,Ref. 179)" F) = 1.5 Hz;J(H-2, F') = 23.8Hz;H-3= 4.62p.p.m.; H-2= 4.39p.p.m.;J(H-2, J (H-3, F) = 1.5 Hz;J (H-3, F') = 0.9Hz;J (H-3, H-4)= 9.3Hz;6F-1 = -79.0p.p.m.; 6F-2 = -76.6 p.p.m.; J (F, F')= 32.8Hz " Partial "C-n.m.r. data also given: C-1 = 157.7 p.p.m., J (C, F) = J (C, F') = 293.7 Hz; C-2 = 78.9 p.p.m., J ( C , F) = 24.0 H z ; J ( C , F') = 16.2 Hz; C-3 = 73.2 p . p . m . . J ( C ,F) = 8.7 H z ; J ( C , F') = 0.0 Hz. (183) W. J. Lloyd and R. Harrison,Carbohydr. Res., 26 (1973)91-98. (184) E. M.Acton,M.Keyanpour-Rad,J. E. Christensen,H.H.Tong, R.P.Kwok,and L.Goodman,Carbohydr. Res., 22 (1972)477-486. (185)A.A.Akhrem,N.B. Khripach,and I. A. Mikhailopulo,Carbohydr. Res., 50 (1976) ~6-~8.
RENE CSUK AND BRIGITTE I. GLANZER
I60
TABLELVIII W-N.m.r. Data for Hexopyranosyl Fluorides Compound
c-1
c-2
c-3
c-4
c-5
C-6
JFJ
JFJ
JFJ
JF,~
JF,S
JF,~
2,3,4,6-Tetra-0-scetyl-~-altropyranosyl fluoride a anorner 104.3 67.7 66.2 64.0 66.4 226.7 38.8 0.9 0.5 2.4 p anorner 105.0 67.1 67.7 64.5 74.7 1.1 227.4 22.9 2,3,4,6-Tetra-0-acetyl-~-galactopyranosyl fluoride a anorner 66.9 104.3 67.3 67.3 68.8 228.3 24.1 3.7 p anorner 107.2 69.2 70.1 66.6 71.3 1.2 217.3 24.9 10.5 4.7 D-Glucopyranosyl fluoride a anorner 69.4 108.2 71.9 73.3 75.0 222.2 24.8 2.9 p anorner 110.0 "76.0 "73.6 69.9 "76.9 211.3 22.1 2.2 4.3 2,3,4,6-tetra-O-acetyla anomer 67.I 103.7 69.9 69.2 69.7 228.9 24.3 4.4 p anorner 106.3 71.3 71.9 67.6 72.1 219.4 29.3 8.8 4.46 3,4,6-tri-O-acetyl-2-O-methyl(Y anorner 103.9 78.4 71.0 67.4 69.5 229.9 23.4 4.4 p anorner 108.4 80.3 72.5 67.7 71.3 217.4 24.9 10.6 4.8 2,4,6-tri-O-acetyl-3-O-rnethyia anomer 103.9 72.0 77.7 68.4 70.0 227.4 24.7 4.6 p anorner 106.1 71.0 79.6 67.9 72.1 218.3 27.8 5.9 3.8
s
References
62.0
C
28
63.2 2.1
C
28
61.1
C
28
61.4
C
28
61.O
D
28
61.4
D
24,28
61.0
C
28
61.9
C
24,28
61.3
C
28
61.5
C
28 e
61.4
C
28
62.2
C
28 (continued)
161
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLELVIII (continued)
Compound c-1 c-2 JF,~
JF,~
c-3
c-4
C-5
C-6
JF.3
JFA
JFS
JF,~
D-Mannopyranosyl fluoride 2,3,4,6-tetra-O-acetylQ anomer 104.7 67.6 68.1 65.0 70.8 223.1 39.7 1.8 3.1 p anomer 104.1 67.8 68.4 66.4 72.7 223.6 25.0 5.9 4.4 3,4,6-tri-O-acetyl-2-O-methyl-a104.6 75.9 70.1 64.8 70.0 35.2 I .o 224. I 2.9 2,4,6-tri-O-acetyl-3-O-methyl-a66.4 70.9 105.0 65.9 76. I 221.2 39.6 2.9 2,3,4,6-Tetra-0-acety1-a-~-talopyranosyl fluoride 104.5 64.6 65.4 65.1 65.8 224.7 36.6 2.9 1.8
S
References
61.7
C
28
62.7
C
28
61.4
C
28
62.0
C
28
61.8
C
28
The assignments may have to be reversed. Ref. 28 reported a coupling of 2.1 Hz. J (F, OMe) =
Hz.
TABLELIX W-N.m.r. Data for 2(or J)-Deoxy3(or 3)-fluorohexo-pyranoses and -pyranosides
Compound c-1 (2.2 JFJ
JF.Z
c-3
c-4
C-5
C-6
JF.3
JF,~
JF,S
JF.~
1,3,4,6-Tetra-~-acetyl-2-deoxy-2-fluoro-a-~-gdactopyranose 89.0 84.1 68.2 67.8 68.6 61.0 22.3 191.1 18.9 7.5 Methyl 2-deoxy-2-fluoro-~-gdactopyranoside p anomer 101.2 91.6 71.3 69.3 75.4 60.9 23.2 179.4 17.1 8.5 3,4,6-tri-O-acetyl-p101.6 88.0 71 .O 67.7 70.6 61.1 22.0 186.8 20.8 8.5 2-Deoxy-2-fluoro-~-glucopyranose Q anomer 90.9 91.5 72.4 70.4 72.5 61.6 21.4 185.9 17.5 8.0 1.3
S
References
C
49,50
D
26
C
26
D
24,57 (continued)
RENE CSUK AND BRIGITTE I. GLANZER
I62
TABLELIX (continued) Compound
c-1
c-2
c-3
c-4
c-5
C-6
JF,~
JF,~
JFJ
JF,~
JFb
JF,~
77.3 1.2
61.8
D
2437
70.0
61.8
C
4930
73.6
61.8
D
24,63, 64
77.3
62.0
D
24,63, 64
73.1
61.7
C
49,50
C
64
A
65
A
65
C
186
C
I86
D
26,186
C
26,186
C
69
p anomer 94.7 94.1 75.3 70.6 23.0 183.1 17.3 8.2 I ,3,4,6-tetra-O-acetyl-a88.8 86.6 71.0 67.9 21.8 194.2 19.4 7.5 2-Deoxy-2-fluoro-D-mannopyranose a anomer 92.5 91.6 70.7 68.1 29.6 172.2 17.5 I .4 p anomer 93.6 92.6 73.1 67.9 15.8 180.0 17.6 1.5 1,3,4,6-tetra-O-acetyl-P90.4 86.5 71.3 65.0 15.4 191.2 17.1
s
References
Benzyl3,4,6-tn-O-benzyl-2-deoxy-2.luoro-fi-~-mannopyranoside 97.0 86.9 80.7 15.9 188.0 18.3 Methyl 3-deoxy-3-fluoro-fi-o-allopyranoside 102.0 67.4 93.7 70.3 74.5 62.0 2.9 16.I 176.0 16.1 6-O-pivaloyl-p101.8 67.4 93.4 70.2 72.0 63.7 3.0 17.6 177.9 16.1 2.9 1,2,4,6-Tetra-O-acetyl-3-deoxy-3.luoro-~-gdactopyranose a anomer 89.7 85.4 8.6 192.9 p anomer 91.5 68.9 88.7 66.7 71.5 61.1 11.0 19.5 195.3 17.1 3.0 2.4 Methyl 3-deoxy-3-fluoro-~-gdactopyranoside p anomer 103.2 69.5 93.2 67.0 74.0 60.7 11.0 19.5 183.1 17.1 7.3 3.6 2,4,6-tri-O-acetyl-p101.3 69.7 88.8 66.9 69.8 61.2 11.0 19.5 192.9 17.1 6.1 2,4-di-O-benzoyl-6-0-(bromoacetyl)a anomer 97.7 70.0 85.9 68.8 66.3 63.8 6.1 8.6 18.3 192.9 17.1
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
163
TABLELIX (continued)
Compound c-1 c-2
References
c-3
c-4
C-5
C-6
JFS
JF,~
JF,~
JF.6
67.8 17.6
70.2 6.2
63.4 3.1
C
69
93.5 71.2 96.2 69.1 10.9 16.8 178.6 17.6 p anomer 96.4 73.8 97.8 69.1 12.4 17.2 180.5 17.6 3-Deoxy-3-fluoro-~-mannopyranose a anomer 94.2 68.9 92.3 65.4 7.0 15.0 183.0 18.0 p anomer 93.0 69.5 93.7 65.1 11.0 17.0 183.0 19.0
72.0 7.3
61.4 1.5
D
24
65.8 8.2
61.6 1.9
D
24
72.0 6.0
60.7
D
187
74.8 7.0
60.7
D
187
JF.I
JF.1
S
p anomer 101.7 9.5
70.6 18.9
88.9 195.8
3-Deoxy-3-fluoro-~-glucopyranose a anomer
(186) P. KovBt and C. P. J. Glaudemans, Curbohydr. Res., 123 (1983) 326-331. (187) J. R. Rasmussen, S. R. Tafuri, and S. T. Smale, Curbohydr. Res., I16 (1983) 21-29.
TABLELX W-N.m.r. Data for 4(or 6)-Deoxy4(or 6)-fluorohexo-pyranosesand -pyranosides
Compound c-1 c-2
c-3
c-4
JF,~
JFJ
JF.~
JFJ
c-5
4-Deoxy-4-fluoro-~-gdactopyranose a anomer 93.6 69.6 “69.2 91.7 “70.5 2.2 17.6 177.0 17.6 p anomer 97.4 73.1 72.8 90.8 74.8 1.1 18.0 177.7 17.3 Methyl 4-deoxy-4-fluoro-~-galactopyranoside a anomer 100.9 69.6 69.7 91.8 71.9 2.6 18.0 177.4 17.6 p anomer 90.9 75.0 104.9 72.0 73.0 178.2 17.6 17.9
C-6
S
61.3 5.5
D
24
61.1 5.5
D
24
61.5 5.5
D
65,188
61.3 5.1
D
26,188
References
(continued)
RENk CSUK AND BRIGITTE I. GLANZER
164
TABLELX (continued) Compound c-1
c-2
c-3
c-4
c-5
C-6
JFJ
JFJ
JFJ
Jp.4
JF3
JF,~
2,3,6-tn-O-acetyla anomer 97.3 67.9
S
References
“66.7 17.7
87.1 185.3
“68.3 17.7
61.9 5.9
C
50
“70.8 18.3
85.9 185.6
“71.8 17.1
61.4 4.9
C
26
78.9 86.0 73.5 17.9 17.7 182.9 2,3-di-O-benzyl-6-0-trityl-p104.4 78.9 79.0 86.2 72. I 17.1 17.1 184.3 4-Deoxy.4-fluoro-D-glucopyranose a anomer 93.2 72.2 a72.3 90.5 “70.1 1.4 8.3 17.6 179.9 23.9 p anomer 97.1 74.9 “75.0 90.3 “72.3 1.4 8.8 18.0 180.0 24.5 4-Deoxy.4-fluoro-~-mannopyranose a anomer 69.9 94.0 71.4 68.7 88.5 9.0 18.0 176.0 24.0 p anomer 73.5 93.8 71.7 71.3 88.3 11.0 18.0 176.0 24.0 Methyl 4-deoxy-4-fluoro-a-~-tdopyranoside 102.0 69.9 66.7 90.0 70.0 17.6 16.1 179.0 Methyl 6-deoxy-6-fluoro-~-gdactopyranoside p anomer 104.0 70.6 72.6 68.4 73.4 20.8 7.3 2,3,4-tri-O-acetyl-p101.8 68.6 70.1 66.9 71.3 23.2 6.1 6-Deoxy-6-fluoro-~-glucopyranose a anomer 93.5 72.6 73.9 69.8 71.5 0.7 6.6 17.2 p anomer 97.3 75.3 76.8 69.7 75.6 6.9 18.7
60.9 5.3
D
26,76 1886
61.6 2.4
C
26
61.2
D
24
61.4
D
24
60.5
D
187
60.4
D
187
60.5 7.4
A
65
83.1 164.8
D
26
80.7 171.5
C
26
83.7 167.2
D
24
83.5 167.6
D
24
p anomer
101.7
68.6
2,3-di-O-benzyl-p104.6 79.0
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
165
TABLELX (continued) Compound c-1 c-2 JF,l
JFJ
S
References
84.8 168.4
A
27,77
82.3 170.9
A
65,77
82.2 170.6
A
65
82.5 170.6
A
65
82.5 170.6
A
65
83.5 170.6
A
65
82.8 170.6
A
65
83.4 170.6
A
65
c-3
c-4
c -5
C-6
JF.3
JF,~
JF,S
JF,~
Methyl 6-deoxy-6-fluoro-~-glucopyranoside a anomer 102.0 73.7 75.5 71.0 73.0 6. I 17.1 /3 anorner 103.8 73.5 76.7 69.0 74.7 7.3 18.3 p-Nitrophenyl6-deoxy-6-fluoro-/3-~-glucopyranoside 100.5 73.6 76.9 68.9 75.5 7.4 17.6 Phenyl6-deoxy-6-fluoro-~-glucopyranoside a anomer 98.5 72.5 74.2 69.4 72.0 4.4 13.2 /3 anomer 101.0 73.7 77.0 69.1 75.2 7.4 17.6 Methyl 6-deoxy-6-fluoro-or-D-mannopyranoside 102.2 72.6 71.5 67.3 72.5 7.4 19.1 2,3-di-O-rnethyl98.9 76.4 81.6 65.4 72.3 7.4 17.6 2,3-O-isopropylidene79.9 76.5 68.6 70.1 99. I 7.3 17.6 * The assignments may have to be reversed.
Ref. 188 reported some data for the a anomer.
(188) J. E. Nam Shin, A. Maradufu, J. Marion, and A. S. Perlin, Carbohydr. Res., 84
(1980) 328-335.
TABLELXI UC-N.m.r. Data for Hexofuranogl Fluorides and Deoxyfluorohexofuranoses Compound c-1 c-2 JFJ
JFS
c-3
C-4
c-5
C-6
JFJ
JF.4
JFJ
JF,~
76.7 1.2
67.6 0.7
62.4
D-Glucofuranosyl Ouoride 2,3,5,6-tetra-O-acetyla anomer 106.9 78.2 73.1 234.2 19.6
S
C
References
28 (continued)
RENE CSUK AND BRIGITTE I. GLANZER
166
TABLELXI (continued)
Compound
References
c-1
c-2
c-3
c-4
c-5
C-6
JF,I
JF,Z
JFS
JF.~
JF,S
JF,6
80.4 2.5
68.2
62.5
C
28
76.8 1.2
67.8 0.9
62.6
C
28
80.1 2.4
68.5
62.8
C
28
81.1
68.7 1.2
62.5
C
28
81.9 2.6
69.3
63.1
C
28
69.8 0.9
78.0 2.1
67.7
62.4
C
28
68.3
77.9 2.4
67.1 1.2
62.2
C
28
C
28
C
89,89a
C
89,89a
C
2530
D
91
D
91
p anomer 111.5 79.0 71.7 228.5 35.4 3,5,6-tri-0-acetyl-2-O-methyla anomer 107.7 86.2 74.0 233.8 18.9 p anomer 112.2 87.0 71.6 226.5 31.4 2,5,6-tri-0-acetyl-3-O-methyla anomer 106.7 77.1 77.7 231.6 19.5 p anomer 112.3 77.8 81.7 227.3 34.5 0.7 D-Mannofuranosyl fluoride
1.5
S
(1
3,5,6-tri-O-acetyl-2-O-methyl-
a anomer 112.6 76.0 225.2 36.0 p anomer 106.5 71.6 236.8 20.1
2,5,6-tri-O-acetyl-3-O-methyl-~-
1.5
62.1 78.1 68.4b 106.7 80.7 66.3b 234.4 20.5 2,3 : 5,6-di-O-isopropylidenea anomer 66.0 72.6 82.6b 113.7 84.7 78Sb 221.5 41.8 p anomer 81.1b 66.5 73.6 107.5 81.2 77.6b 235.6 22.0 1,2 :5,6-Di-O-isopropylidene-3-deoxy-3-fluoro-~-~-glucofuranose 104.8 82.3 93.5 80.4 71.7 66.9 33.8 183.0 19. I 7.4 5-Deoxy-5-fluoro-D-glucofuranose a anomer 97.5 76.4 75.7 76.4 92.0 62.0 28.4 167.7 19.1 p anomer 103.1 81.0 75.3 79.2 92.0 62.3 28.4 167.7 20.5
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
167
TABLELXI (continued) Compound c-1 c-2 JFJ
JF,Z
c-3
c-4
c-5
C-6
JFJ
JF,~
JF,S
JF,6
78.8 30.9
91.5 167.6
62.9 19.1
A
91
80.2 17.7
93.6 172.9
61.8 20.0
D
91
77.3 17.7
94.5 170.6
61.8 20.0
D
91
80.7 19.1
94.6 170.6
62.0 22.0
A
91
1,2-O-isopropylidene-a106.1 86.3 74.7
5-Deoxy-5-fluoro-~-idofuranose a anomer 102.6 81.1 75.2 5.8 p anomer 96.7 76.5 75.2 5.8 1,2-O-isopropylidene-p105.7 86.4 75.2 8.8 J (F, OMe)
=
S
0.9 Hz. * The assignments may have to be reversed
TABLELXII W-N.m.r. Data for Fluorinated Pentopyranose Derivatives
2,3,4-Tri-O-acetyl-P~-arabinopyranosyl fluoride 104.6 67.5 68.1 66.4 62.4 C 28 227.1 26.4 2.8 2,3,4-Tri-0-acetyl-~-xylopyranosylfluoride a anomer 103.8 70.3 68.8 68.0 60.1 C 28 228.5 23.4 4.4 p anomer 105.3 67.0 67.1 66.8 60.6 C 28 222.8 36.0 2.8 0.6 3.4 l,3,4-Tr~-O-acetyl-2-deoxy-2-fluoro-&o-arbinopyranose 89.5 84.3 67.8 69.0 62.5 C 49,50 22.1 191.1 18.7 6.8 1,3,4-Tri-~-acetyl-2-deoxy-2-fluoro-cr-~-l~opyranose C 49,50 89.6 79.6 68.6 67.7 61.8 19.1 192.7 17.6 2.9 1,3,4-Tri-0-acetyl-2-deoxy-2-fluoro-~-ribopyranose a anomer 88.9 84.0 67.2 “65.3 “61.0 C 49,50 20.0 198.1 16.7 (continued)
References
RENE CSUK AND BRIGITTE I. GLANZER
I68
TABLELXII (continued) Compound C-1 C.2 JFZ
JFJ
C-3
C-4
C-5
JFJ
JFA
JFJ
S
References
p anomer 90.8 84.7 66.0 66.1 62.8 C 101 30.5 189.2 18.3 1,3,4-Tri-0-acetyl-2-deoxy-2-fluoro-cu-~-xy~opyrmose 88.8 86.6 70.2 68.3 60.6 C 49,50 20.6 194.4 19.1 7.4 Methyl 4-deoxy-4-fluoro-~-arahinopyranoside a anomer 60.1 D 65 99.4 67.9 67.5 90.3 19.1 173.5 19.1 p anorner 104.6 71.7 72.2 89.4 64.0 C 65 22.0 177.9 20.6 a
The assignments may have to be reversed.
TABLELXIII W-N.m.r. Data for Fluorinated Pentofuranose Derivatives Compound C-1 C-2 JFJ
JFZ
C-3
C-4
C-5
JFS
JF.4
JF.S
o-Arabinofuranosyl fluoride 2,3,5-tri-O-benzoyl-a-~112.7 80.9 76.7 84.4 63.5 225.8 40.3 2,3 ,S-tri-O-benzyl-a-~113.5 224.6 2,3,5-tri-O-benzyl-P-~108.3 228.8 o-Lyxofuranosyl fluoride 5-0-benzoyl-2,3-benzoxonium-a114.2 97.1 95.5 84.3 66.7 229.4 47.1 2,3,5-tri-O-benzoyla anomer 112.3 75.7 70.8 78.3 62.9 224.7 37.4 1.8 1.8
S
References
C
28
C
105,106 a
C
105
F
107
C
28 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES TABLELXIII (continued) Compound C-1 C-2 JF.I
J F ~
C-3
C-4
C-5
JFJ
JFR
JF.S
S
References
p anomer 107.1 72.7 68.5 79.0 63.1 C 28 236.1 20.5 1.2 2.6 D-Ribofurnnosyl fluoride 2,3-acetoxonium-5-0-acetyl-P115.5 98.1 97.0 88.5 69.6 F 107 230.9 47.1 2.9 2,3,5-tri-O-benzoyla anomer 107.4 71.9 69.6 82.9 63.6 C 28 234.4 20.5 p anomer 112.4 75.0 71.4 81.3 64.3 C 28 225.5 35.9 1.5 2.9 0.5 2.3,s-tri-0-benzyla anomer 108.5 C 106 232.5 p anomer 112.4 C 106 224.0 2,3,S-Tn-O-benzoyl-cu-~-xylofurnnosyl fluoride 112.3 80.2 73.8 81.6 63.2 C 28 228.0 36.8 l-O-Acetyl-2-deoxy-2-fluoro-S-O-( methoxymethyl)-a-~ribofurnnose 94.2 88.1 69.9 84.7 66.7 C 49,50 16.0 200.3 17.0 3.0 3-Deoxy-3-fluoro-1,2-O-isopropylidene-cu-~-~~o-pentodinldo-1,4-furanose 105.9 94.9 197.0 C I I4 182.6 6.9 " Ref.
105 reported data for the
D
enantiomer.
169
RENI? CSUK AND BRIGITTE I. GLANZER
I70
TABLELXIV W-N.m.r. Data for Fluorinated Sugar Acids and Lactones Compound C-1 C-2 JF.l
JF,Z
C-3
C-4
C-5
C-6
JFS
JF,4
JF5
JF.6
References
S
5-Deoxy-5-fluoro-a-~-glucofuranurono-6,3-lactone 1,2-O-isopropylidene107.6 82.7 81.7 76.6 86.2 168.0 C 5.9 14.7 206.9 23.8 5-Deoxy-5-fluoro-&~-idofuranurono-6,3-lactone 1,2-O-benzylidene105.1 82.3 84.5 81.0 87.5 169.0 C 28.2 179.8 20.0 1,2-O-isopropylidene106.5 82.2 85.1 80.0 87.3 169.1 C 28.0 185.3 20.6
91
125 91
TABLELXV W-N.m.r. Data for Fluorinated Amino Sugars and Their N-Containing, Synthetic Precursors
Compound C-1 C-2 JF.1
JF.Z
C-3
C-4
C-5
C-6
JF,3
JF.4
JF.5
JF,6
S
References
3-Azido-4,6-0-benzylidene-3-deoxy-~-~-allopyranosyl fluoride 108.5 76.7 61.4 77.1 64.1 67.8 C 214.9 22.9 9.8 4.6 Benzyl 2-fluoro-cu-D-dtropyranoside 3-azido-4,6-O-benzylidene-2,3-dideoxy96.4 88.0 57.7 75.9 59.3 69.2 C 34.3 174.9 28.9 3-benzamido-2,3,6-trideoxy96.6 87.2 50.3 70.4 65.4 17.4 C 31.0 178.6 26.9 Methyl 2,3,6-trideoxy-2-fluoro-cr-~-altropyranoside 3-amino64.5 17.6 C 98.5 89.1 50.6 67.8 32.0 176.0 24.0
127
I27 132
133
3-(trifluoroacetarnido)-
97.7 86.1 49.9 68.7 64.4 30.2 178.0 28.1 3-benzamido-4-O-benzoyl-6-bromo98.5 86.6 47.0 67.7 67.0 30.7 179.8 28.3
17.4
C
133
31.9
C
133 (conrinued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
I7 I
TABLELXV (continued)
3-benzamido-4-0-benzoyl98.4 86.9 46.9 70.1 62.7 17.5 C 133 18.1 8.3 30.8 179.2 Benzyl 2,3,6-trideoxy-2-fluoro-fi-~-galactopyranoside 3-benzamido100.3 89.6 54.0 72.0 71.8 16.1 B 132 22.8 187.4 17.8 8.1 4-0-benzoyl-3-(trifluoroacetamido)99.8 88.2 53.1 72.2 71.1 16.4 C 127 22.3 189.1 18.7 7.1 Methyl 2,3,6-trideoxy-2-fluoro-/3-~-galactopyranoside 3-amino101.6 92.7 55.6 72.2 71.9 16.3 C I33 18.1 8.3 23.0 180.4 3-(trifluoroacetamido)55.5 71.2 72.1 16.4 C 133 102.6 89.1 22.4 184.0 16.1 7.8 3-benzamido-4-0-benzoyl102.3 88.9 52.7 73.2 70.9 16.4 C I33 21.5 187.5 17.5 7.8 Methyl 3-benzamido-4-O-benzoyl-2,3,6-tndeox~2-fluoro-c~-~-u~u~i~ohex-5-enopyranoside 100.1 86.9 48.5 66.7 149.8 99.5 C 133 180.1 27.3 31.5 Methyl 6~azido-3,6-dideoxy-3-fluoro-fi-~-allopyranoside 102.0 70.4 93.5 68.2 73.8 52.0 A 65 18.0 3.0 0.0 3.4 17.0 177.7 Benzyl 4,6-0-benzylidene-2,3-dideoxy-3-fluoro-c~-~-glucopyranoside 2-azido80.1 62.6 68.8 C 127 98.0 62.3 88.7 8.8 17.4 189.1 17.2 7.6 2-benzamidoP 132 99.0 54.5 89.5 80.9 63.4 69.2 9.0 17.1 191.0 16.5 7.5 Methyl 4-azido-4,6-dideoxy.6-fluoro-c~-~-glucopyranoside 100.5 72.8 73.5 61.7 69.2 82.7 A 65 5.9 17.6 172.0 3-Acetamido-2,3,5,6-tetradeoxy-5-fluoro-fi-~~-~i~o-hexofuranose 99.8 40.2 49.6 85.3 91.7 16.3 C 140 20.8 167.2 22.0 Methyl 3-aceta~do-2,3,5,6-tetradeoxy-5-fluoro-~~-~i~o-hexofuranoside a anomer 103.6 39.3 48.4 86.1 90.3 16.8 C 140 43.9 180.7 22.0 (continued)
RENB
I72
CSUK AND BRIGITTE I. GLANZER TABLELXV (continued)
Compound C-1 C-2 JF.1
JF.2
p anomer 105.6 39.3
C-3
C-4
C-5
C-6
JF,3
JF.4
JFJ
JF,6
50.7
88.3 20.7
90.3 180.7
16.8 22.0
S
References
C
140
TABLELXVI W-N.m.r. Data for Branched or Deoxy Fluorinated Monosaccharides
Compound C-1 C-2 JF.1
JF3
C-3
C-4
C-5
C-6
JF,3
JF.4
JF5
JF.6
~
S
References
~~
Methyl 4,6-0-benzylidene-2-deoxy-3-C-[ (ethoxycarbony1)-(fluoromethyl)]-a-~-ribbo-hexopyranoside (I?) isomer 98.2 36.2 71.5 77.2 58.7 69.2 C 189 3.3 19.5 (S)isomer 98.4 33.8 71.0 77.4 58.9 69.1 C 189 1.4 22.0 1.1 b Methyl [benzyl 2-(benzyloxycarbonyl)amino-2,3,4-trideoxy-5-fluoro-aD-erythro-hex-3-enopyranosid]uronate 94.6 46.9 132.1 122.6 97.3 166.0 B 126 8.4 27.5 224.3 37.4 1-0-Acetyl-2,3,5,6-tetra-O-benzoyl-4-fluoro-~~-g~actofuranose 98.8 79.7 75.5 70.1 62.2 C I59 0 21.1 35.7 2.2 1-0-Acetyl-2,3,5,6-tetra~O-benzoyl-4-fluoro-~-~-glucofuranose 102.0 79.0 77.2 120.7 70.6 62.5 A 159 41.2 232.1 26.4
1-0-Acetyl-2,3,5-tri-O-benzoyl-4-fluoro-a-~-lyxofuranose
99.4 74.9 74.6 118.2 62.4 C 159 2.5 0.0 42.0 232.7 30.2 l-O-Acetyl-2,3,5-tri-O-benzoyl-4-fluoro-~-~-nbofuranose 98.3 73.1 70.1 114.4 62.8 - C 159 0.0 0.0 18.0 237.5 44.4 Methyl 2,4-di-0-benzoyl-6-0-(bromoacetyl)-3-deoxy-3-fluoro-a-~galactopyranosyl chloride 91.1 69.3 85.5 67.9 69.7 62.9 C 69 9.1 18.9 193.1 17.1 4.7 4.0 2,3,4-Tri-0-acelyl-6-deoxy-a-~-glucopymnosyl fluoride 103.8 70.8 69.5 72.7 67.9 17.1 C 28 227.7 24.7 4.6 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES TABLELXVI (continued)
Compound C-1 C-2 JF.2
JF,l
C-3
C-4
C-5
C-6
JF,3
JF.4
JFJ
JF.6
S
References
2,3,4-Tri-O-acetyl-6-deox~cu-~-mannopyranosyl fluoride 104.7 67.8 68.1 69.8 68.7 17.1 C 221.3 41.3 2.1 3.1
28
* CO: 167.7 p.p.m.; J (C-F) = 24.4 Hz; CHF (of fluoromethylene): 88.2 p.p.m.; J (C-F) = 194.1 Hz; partial IH-n.m.r. data also given. CO: 167.5 p.p.m.; J (C-F) = 23.8 Hz; CHF (of fluoromethylene): 86.2 p.p.m.; J (C-F) = 186.8 Hz; partial IH-n.rn.r. data also given.
(189) S. Brandange, 0. Dahlman, and L. Morch, J . Am. Chem. Soc., 103 (1981) 4452-4458.
TABLELXVII W-N.m.r. Data for Fluorinated Ketopyranoses and Derivatives
Compound C-1 C-2 JFJ
JFJ
C-3
C-4
C-5
C-6
JFJ
JF.4
JF.5
JF.6
S
References
l-Deoxy-l-fluoro-2,3 :4,5-di-O-isopropylidene-~-fructopyranose 82.2 101.2 69.9 70.2 70.9 61.1 C 160 174.0 21.5 2.0 1.o 4-Deoxy-4-fluoro-~~-fructopyranose 63.6 98.6 66.2 91.6 67.5 62.7 D 161 1.6 9.7 18.3 180.1 16.6 7.0 4-Deoxy-4-fluoro-a-~-sorbopyranose 64.2 99.1 69.8 96.8 68.8 61.8 C 161,190 10.0 17.0 178.0 17.0 10.0
~-~eox~4-fluoro-1,2-O-~sopropyl~dene-~-~-tagatopyr~ose
72.3
105.4
67.4 26.0
90.7 178.0
64.3 17.0
61.8
C
190
59.9 26.0
C
190
5-Deoxy-5-fluoro-cu-~-sorbopyranose 64.3
98.4
71.0 7.0
73.2 17.0
" An additional coupling, J (F,Me)
90.2 178.0 = 2.9 Hz, is
observed (6 Me
=
24.7).
(190) G. V. Rao, L. Que, Jr., L. D. Hall, and T. P. Fondy, Carbohydr. Res., 40 (1975) 311-321.
173
RENE CSUK AND BRIGITTE I. GLANZER
I74
TABLELXVIII W-N.m.r. Data for Mono- and Di-fluorinated Ketofuranose Derivatives Compound C-1 C-2 JYJ
JF,Z
C-3
C-4
C-5
C-6
JFJ
JF,~
JFJ
JF,~
S
References
C
I63
C
I63
A
I64
A
164
1,3,4,6-Tetra-O-acety~-~-fructofuranosyl fluoride
a anomer 61.2 117.5 78.2 83.5 76.7 62.7 28.8 226.8 46.0 1.5 0.2 0.5 p anomer 61.7 113.9 75.0 80.2 74.7 63.6 43.7 232.8 20.9 2.8 0.4 Methyl 1-deoxy-1-fluoro-D-fructofuranoside a anomer 78.6 108.0 81.3 79.4 86.3 62.8 170.9 20.8 p anomer 81.6 102.7 79.1 76.7 83.4 63.7 174.6 19.5 3,4,6-tri-O-benzoyI-p-
C 164 173.3 19.3 6-Deoxy-6-fluoro-2,3-O-isopropylidene-l-O-p-tolyls~onyl-~-~-fructofuranose 68.2 113.9 83.6 74.9 86.7 81.8 C 164 4.9 20.8 170.9 1,6-Dideoxy-1,6-difluoro-2,3-O-isopropylidene-~-~-fructofuranose 81.2 113.3 86.8 75.2 86.7 82.2 C 164 172.0 23.2 a 4.9 20.8 177.0 b Methyl 1,6-dideoxy-1,6-difluoro-~-fructofuranoside a anomer 79.3 107.4 81.9 78.0 82.9 83.5 A 164 172.1 20.8 b 7.3 19.5 170.9 p anomer 81.4' 102.9 79.0 75.3 81.3' 83.6 A 164 174.5 19.5 0 7.3 18.3 172.1 b Coupling to fluorine at C-1, Coupling to fluorine at C-6. The assignments may have to be reversed.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
TABLELXIX W-N.m.r. Data for Difluorinated Monosaccharides, Including Anhydro and Unsaturated Derivatives Compound
C-1
C-2
C-3
C-4
C-5
C-6
JF.1
JF,2
JF.3
JF,4
JF.5
JF.6
JF.1
JF.2
JFJ
JF.4
JFJ
JF,6
S
References a
b
3,6-Dideoxy-3,6-difluoro-~-~-allopyranoside methyl 102.1 70.7 93.6 ‘66.3 ‘73.0 83.1 A 65,77 4.3 17.2 177.0 d25.0 7.9 ‘4.3 20.0 170.9 phenyl 65 99.0 70.0 93.6 73.1 65.8 82.5 A 4.4 17.0 177.9 17.6 8.0 2.9 17.6 172.0 Methyl 4,6-dideoxy-4,6-difluoro-~-galactopyranoside (Y anomer 77 102.5 ‘69.9 ‘70.5 92.8 ‘71.5 84.9 A 178.2 6.1 6.1 167.2 p anomer 77 105.1 ‘71.8 ‘72.5 89.8 ‘72.6 82.6 A 180.7 6.1 6.7 167.9 Methyl 4,6-dideoxy-4,6-difluoro-cu-~-talopyranoside 102.0 69.4 65.3 ‘81.9 67.5 %9.6 C 27,77 16.1 ’158.0 22.1 87.4 7.4 17.6 172.0 3,6-Anhydro-6,6-diBuoro-a-~-glucofuranose I ,2-O-benzylidene125 105.1 84.9 84.1 82.1 74.2 128.7 C 6.0 31.0 265.0 26.0 260.0 1,2-O-isopropylidene125 106.1 83.2 83.4 79.6 72.9 127.3 C 1.8 2.0 6.2 30.0 264.0 1.6 25.0 248.0 3,6.Anhydro-6,6-difluoro-1,2-~-isopropylidene-~-~-idofuranose I25 106.1 85.5 86.7 82.9 74.9 130.2 C 2.0 3.0 37.0 259.0 22.0 259.0 5,6-Dideoxy-6,6-difluoro-1,2-O-isopropylidene-u-~-xylo-hex-5-enofuranose 3-0-benzyl73.7 75.1 157.2 C 179 26.2 292.5 8.8 0.0 15.9 289.0 (continued)
175
RENE CSUK AND BRIGITTE I. GLANZER
176
TABLELXIX (continued)
3-O-methyl-
73.4 74.9 157.1 C 179 27.0 292.4 9.2 0.0 10.8 288.5 5,6-Dideoxy-6,6-diffuoro-l,2-O-isopropylidene-3-O-methyl-~-~-/y~o-hex-5enofuranose 73.2 78.6 157.6 C 179 22.5 290.3 7.5 0.0 16.2 290.3 5,6-Dideoxy-6,6-diffuoro-l,2-O-isopropylidene-3-O-methyl-~-~-ribo-hex-5enofuranose 71.8 78.0 158.4 C 179 25.3 293.9 8.7 0.0 16.5 290.0 6-Chloro-5,6-dideoxy-5,6-difluoro-l,2-O-isopropylidene-3-O-methyl-a-D-~/ohex-5-enofuranose ( E ) isomer 104.6 85.1 81.8 73.9 101.9 146.3 C 178 12.4 306.7 (Z) isomer 104.7 85.2 81.90 76.7 101.4 147.0 C 178 8.3 23.8 301.2 Methyl 5,6-dideoxy.6,6-difluoro-2,3-O-isopropylidene-a-~-ri~o-hex-5-enofuranoside 109.6 85.6 79.7 85.4 80.4 156.8 C 178 h 7.4 11.9 20.5 291.5 0.0 17.4 3,5,6-Trideoxy-6,6-diffuoro-l,2-O-isopropylidene-~-~-e~r~ro-hex-5enofuranose 105.2 80.5 39.8 70.8 79.3 157.3 C 178 h 7.8 23.7 288.8 i 0.0 16.5 292.4 a The couplings refer to the “lower”-numbered fluorine atom. The couplings refer to the “higher”-numbered fluorine atom. The assignments may have to be reversed. Ref. 65 reported a coupling of 17.6 Hz. Ref. 65 reported a coupling of 2.9 Hz.f Ref. 77 reported a coupling of 180 Hz (solvent A). * Ref. 77 reported a coupling of 5.5 Hz (solvent A). * Coupling to cis-oriented fluorine atom. Coupling to trans-oriented fluorine atom.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
I77
TABLELXX W-N.m.r. Data for Tri- and Tetra-fluorinated Monosaccharides Compound c-1
c-2
c-3
c-4
c-5
C-6
JFJ
JFJ
JF3
JF.~
JF5
JF,6
JFJ
JFJ
JFJ
JF.~
JFJ
JF,6
JFJ
JFJ
JFJ
JF,~
JF5
JF.6
JFJ
JFJ
JFJ
JF.~
JF,S
JF,6
References
S
3,6-Anhydro-5-deoxy-5,6,6-trifluoro-l,2-O-isopropylidene-cu-~-glucofuranose 106.0 83.8 83.0 77.6 88.1 126.5 C 125 14.0 204.0 266.0 b 4.0 33.0 250.0 b 24.0 22.0 3,6-Anhydro-5-deoxy-5,6,6-trifluoro-l,2-O-isopropylidene-~-~-idofuranose 105.4 86.0 81.7 80.9 89.7 126.7 C 125 L7 3.0 30.0 188.0 258.0 b 42.0 258.0 b 22.0 22.0 3,4,6-Trideoxy-3,4,6-trifluoro-cu-~-galactopyranosyl fluoride 108.95 67.95 89.41 88.09 71.20 81.78 M 182 226.8 53.0 22.7 11.0 22.7 188.7 3.7 e 2.0 18.4 181.7 21.0 b 6.6 21.0 169.3 ' Coupling to fluorine at C-5. Coupling to fluorine at (2-6. Coupling to fluorine at C-I. Coupling to fluorine at C-3. Coupling to fluorine at C-4.
TABLELXXI W-N.m.r. Data for Fluorinated Neuraminic Acid Derivatives Compound
C-1
C-2
C-3
C-4
C-5
C-6
C-7
C-8
C-9
JF.1
JF,Z
JF,3
JF,~
JF,S
JF,6
JF.~
JF,~
JF,~
S
References
Methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,S-dideo~2-nonulosylfluoride)onate ff-D-glyCer0-aD-gUhCt0165.9 106.9 35.9 68.7 49.0 73.4 67.5 69.9 62.3 C 191 30.0 223.6 25.0 8.6 ff-D-glyCer0-P-D - g U h C t O 165.0 108.0 35.5 68.5 48.6 73.2 29.7 231.0 28.3 N-Acetyl-9-deoxy-9-fluoroneuraminic acid 175.5 96.4 39.1 67.8 53.2 71.5 a
67.4
70.4
62.5
C
191 n
68.5 7.2
69.9 17.8
86.4 164.9
D
Partial 'H-n.m.r. data reported, too. 6F = -235.4 p.p.m.
(191) M. N. Sharma and R. Eby, Carbohydr. Res., 127 (1984) 201-210. (192) M. Sharma and W. Korytnyk, J . Carbohydr. Chem., 1 (1982-1983) 311-315.
192 b
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES* BY RENB CSUK**AND BRIGITTEI. GLANZER** Instirute of Organic Chemistry, Technical University of Graz, Graz, Austria I. Introduction ............................................................ 11. Spectroscopy of Fluorinated Monosaccharides ............................. 1. IH-N.m.r. Spectroscopy .............................................. 2. W-N.m.r. Spectroscopy .............................................. 3. I9F-N.m.r. Spectroscopy .............................................. 4. Other Nuclei.. ....................................................... 111. Tables ................................................................. 1. Guide to Tables.. .................................................... 2. Tables .............................................................. Addendum .............................................................
73 74 75 77 78 80 80 80 82 33 1
I. INTRODUCTION Within the past two decades, the importance of nuclear magnetic resonance (n.m.r.) spectroscopy has enlarged tremendously. Its advantages over other methods in the structural and conformational analysis of such complex molecules as natural products , I and particularly with regard to the still-increasing importance of medical investigations2 using n.m.r. techniques, is abundantly evident. Because destruction of the sample is avoided, different n.m.r. experiments can be performed repeatedly, and
* The authors thank Dr. Karl Dax, Institute of Organic Chemistry, Technical University,
Graz,for suggesting that we make such a compilation and for pointing out its potential
practical use. ** Present address: Organisch-Chemisches Institut der Universitat, Winterthurer Strasse 190, CH-8057, Zurich, Switzerland. (1) G. Govil and R. V. Hosur, in E. Diehl, E. Fluck, and R. Kosfeld (Eds.), NMR- Basic
Principles and Progress, Vol. 20, Springer Verlag, Berlin, 1982. (2) K. Roth, NMR-Tomography and -Spectroscopy in Medicine, Springer Verlag, Berlin, 1984. 73 Copyright 0 1988 by Academic Press, Inc. All rights of reproduction in any form reserved.
RENE CSUK AND BRIGITTE I. GLANZER
74
analysis of the spectra is usually convenient, simple, and fast.3This methodology is exceptionally free from artifacts, thus allowing detailed analysis of conformational behavior in solution in comparison with the conformation in the solid state (obtained from X-ray analysis or from a n.m.r. spectrum of the solid4). 11. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
Application of 1H-n.m.r. spectroscopy to such complex molecules as carbohydrate^^.^ in general, and fluorinated monosaccharides7 in particular, soon showed the limits of this methodology, and prompted the development of modifications. Double- and triple-resonance techniques5q6and isotopic labelling of compounds, together with the use of Fourier-transform spectroscopy at very high field-strength now allows acquisition of high-resolution, n.m.r. spectra. Further progress followed the application of two-dimensional* n.m.r. techniques in the carbohydrate field.9 Because of these great improvements, all magnetic nuclei can now be used in n.m.r. analysis of fluorinated monosaccharides,1° including 'H, 13C, 15N,and 19F.Table I gives the relevant, spectroscopic data for these nuclei. TABLEI Comparison of the Relevant Parameters of Different NucleP5 Nuclei
Spin
Natural abundance
H
112 1/2 1/2 112
99.98 1.11 0.37 100
Sensitivity Gyromagnetic Relative Absolute" Rangeb ratio FrequencyC ~~
c
N F
loo0 15.9 1.04 830
~~~
lo00 0.18 0.004
830
20 650 1000 800
2.793 0.702 0.283 2.627
100 25.14 10.13 94.08
a Relative sensitivity: at constant field for equal number of nuclei; absolute intensity: product of relative sensitivity and natural abundance. In parts per million (p.p.m.). For a field strength of 2.3480 tesla.
(3) E. D. Bishop, Annu. Rep. NMR Spectrosc., 1 (1968) 91-134. (4) M. Mehring, Principles of High Resolution NMR in Solids, 2nd edn., Springer Verlag, Berlin, 1983. (5) T. D. Inch, Annu. Rep. NMR Spectrosc., JA (1972) 305-352. (6) L.D. Hall, in W. Pigman and D. Horton (Eds.), The Carbohydrates; Chemistry and Biochemistry, 2nd edn., Vol. IB, Academic Press, New York, 1980, pp. 1299-1326. (7) P. J. Card, J . Carbohydr. Chem., 4 (1985) 451-487. (8) A. Bax, Two-Dimensional Nuclear Magnetic Resonance in Liquids, Reidel, Dordrecht, 1982. (9) L. D. Hall and S. Sukumar, J . Am. Chem. SOC.,101 (1979) 3120-3121. (10) A. A. E. Penglis, Adv. Carbohydr. Chem. Biochem., 38 (1981) 195-285.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
75
1. 'H-N.m.r. Spectroscopy
a. Chemical Shifts.-Introduction of a fluorine atom into an organic molecule causes a significant shift to low-field of the signals of the geminal hydrogen atoms. However, the practical use of this effect, and its interpretation in terms of structure and conformation, remain small.
b. lH-19F Coupling Constants.-The 'H-19F spin-spin coupling is influenced by steric and electronic influences of substituents, both in close proximity to, or remote from, the coupling nuclei. The stereospecific dependences of fluorine-proton couplings compared to the corresponding 'H-lH couplings are much more sensitive to the steric environment, and the coupling constants are of much greater magnitude. Because IH-19F coupling-constants can be readily extracted from the 19F spectrum without interference of proton-proton coupling-patterns, this additional information facilitates even the interpretation of the proton spectra without the need for fluorine decoupling experiments. Geminal Coupling, 3 ('H, 19F). The sign of geminal coupling constants has been determined" and shown to be absolutely positiveI2 and to occur in secondary, carbohydrate-derived pyranoid derivatives in a range lying between 49 and 59 Hertz (Hz), whereas the furanoid counterparts show coupling of 49-66 Hz; where fluorine is attached to sp-hybridized carbon atoms, couplings of some 80 Hz may be observed. An empirical approachI3 for estimating geminal coupling-constants has been described for a limited class of compounds. Irrespective of whether fluorine is axially or equatorially oriented, an increase (-3 Hz) in 2J results upon changing the vicinal substituent from the axial (a) to the equatorial (e) orientation, whereas changing the fluorine atom from equatorial to axial has little or no effect. An exception to the latter occurs in cases where the substituent is a ring-oxygen or -sulfur atom. Vicinal Coupling, 3J (lH, 19F). The signs14 of vicinal couplings were found to be absolutely po~itive,'~ and their angular dependence parallels*0 ranging between 0 and that of proton-proton coupling-c~nstants,~~J~ (11) L. D. Hall, R. N. Johnson, A. B. Foster, and J. H. Westwood, Can. J . Chem., 49 (1971) 236-240. (12) A. D. Barford, A. B. Foster, J. H. Westwood, L. D. Hall, and R. N. Johnson, Carbohydr. Res., 19 (1971) 49-61. (13) L. Phillips and V. Wray, J . Chem. Soc., Perkin Trans. 2 , (1974) 928-933. (14) L. D. Hall and J. F. Manville, Chem. Znd. (London), (1967) 468-469. (15) L. D. Hall and J. F. Manville, Carbohydr. Res., 9 (1969) 11-19. (16) A. Gaudemer, in H. B. Kagan (Ed.), Stereochernistty: Fundamentals and Methods, Vol. 1, Thieme Verlag, Stuttgart, 1977, pp. 44-136. (17) L. D. Hall, J. F. Manville, and N. S. Bhacca, Can. J . Chem., 47 (1969) 1-17.
76
RENB CSUK AND BRIGITTE I. GLANZER
some 30 Hz (compare, Table 11). The value of J (trans) are found to be larger than J (gauche).These couplings depend on the electronegativity of neighboring substituents. Only a few exceptions to the empirical ranges given in Table I1 are known. trans-Vicinal couplings in the pyranose series depend additionally on the nature of the substituents on the carbon atoms to which the coupled nuclei are themselves bound. The coupling constant decreases as the number of oxygen atoms increases. The factors that control gauche, vicinal coupling depend onlo: the presence of a hydroxyl group trans to the C-C bond bearing the coupling nuclei, the presence of an oxygen atom trans to the fluorine atom by way of the coupling pathway, and also on the number of substituted oxygen atoms on the carbon atoms bearing the coupled nuclei. Long-range Coupling, 4J (*H, '9F). The signs" of these coupling constants vary. The signs for 4J (e,e) in the pyranose series are absolutely positive, whereas 4J (e,a) values are negative; 4J (a,a) are again positive.Ia2O These couplings show the same stereospecificity as compared to their correspondingproton-proton couplings and reach their largest magnitude when a planar M (that is, a coplanar W)relationship is adopted.21 Pyranoses and furanoses both show stereoselectivity in their coupling constants. For the latter, there are possible coupling pathways either via the ring-oxygen atom or exclusively via C-C bonds (compare, Table 111).22 sJ ('H,'9F). Although these long-range coupling-constants have been observed for a few compounds, their practical use remains small. An extended "M" arrangement is anticipated to be the favored pathway for
jJ
Ring form Pyranose Furanose
TABLEI1 (W, '9F) Couplings
Orientation
Coupling constant (in Hz)
trans-diaxial
21-30 0-18 14-30 2-1s
gauche trans cis
L. D. Hall, R. N. Johnson, J. Adamson, and A. B. Foster, Can. J . Chem., 49 (1971) 1 18- 123. A. B. Foster, J. H. Westwood, B. Donaldson, and L. D. Hall, Carbohydr. Res., 25 (1972) 228-23 1. A. B. Foster, R. Hems, and L. D. Hall, Can. J . Chem., 48 (1970) 3937-3945. A. B. Foster, R. Hems, L. D. Hall, and J. F. Manville, Chem. Commun., (1968) 158-159. L. D. Hall and P. R. Steiner, Can. J . Chem., 48 (1970) 2439-2443.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
77
TABLE111 41 (IH,
Ring form Pyranose Furanose
19F) Coupling
Constants Coupling constant (in Hz)
Orientation" e, e e, a a, a trans cis
via via via via
oxygenb C-C bonds' oxygenb C-C bonds'
-4-5 -0- 1 -0.5-2.5 5.5-8 -0.7 1.o-2 - 1.7-2.4
-
" The symbol e stands for equatorial, and a for axial. * Corresponds to a coupling of F-1 to H-4. Corresponds to a coupling of F-1 to H-3.
such couplings, and the couplings reach a maximum when the coupled nuclei are trans-coplanar to the bond that is the midpoint of the coupling pathway.23In addition, an oxygen atom in the coupling pathway leads to increased values as compared to an all-carbon pathway.24 6J (IH,19F). There are only a few examples of this long-range coupling; their use in conformational analysis seems to be negligible. 2. 13C-N.m.r. Spectroscopy
a. Chemical Shifts.-I3C-N.m.r. spectroscopy at natural abundance provides insights on structural and conformational behavior in solution, combined with the advantage of less-crowded and more-readily interpreted spectra. An excellent article on 13C-n.m.r. data for monosaccharides has been published in this Series.25In general, fluorine substitution in carbohydrates results in a significant, low-field shifting of the signal of the adjacent carbon a t o ~ n . ~ ~ , ~ ' b. "C-I9F Coupling Constants.-The measurement of these coupling constants, using proton-broad-band decoupling, is facile, and greatly aids in the interpretation and assignment of the spectra. 'J ( I T , 19F).These coupling constants are of negative sign,28and their magnitude depends on several factors: l o (I) The magnitude increases with (23) L.Phillips and V. Wray, J. Chem. Soc., B , (1971)1618-1624. (24) V. Wray, J . Chern. Soc., Perkin Trans. 2 , (1976)1598-1605. (25) K.Bock and C. Pedersen, Adv. Carbohydr. Chem. Biochem., 41 (1983)27-66. (26) P. KovAC and C. P. J. Glaudemans, J . Carbohydr. Chem., 2 (1983)313-327. (27) P. J. Card, J . Org. Chern., 48 (1983)393-395. (28) K. Bock and C. Pedersen, Acra Chem. Scand., Ser. B , 29 (1975)682-686.
78
RENE CSUK AND BRIGITTE I. GLANZER
increase in the electronegativity of the atoms attached to the coupled carbon atom. (2) There is dependence on the orientation of the fluorine atom under consideration, including remote effects. Secondary deoxyfluoroglycopyranoses exhibit such couplings of -225 Hz, glycosyl fluorides of - 180 Hz, and 6-deoxy-6-fluoroglycopyranoses of 165 Hz. 2J ( 13C, 19F).The sign of these couplings28was found, or assumed, to be positive and their magnitude depends to a much smaller extent on the electronegativity of the atoms attached to the coupled fragment than does that of 'J ( I3C, IyF).However, they are much more sensitive to the orientation of these electronegative substituents with respect to the fluorine atom.I0 jJ ( 13C, 19F).This coupling shows the same angular dependences as the corresponding fluorine-proton or proton-proton counterpart,I6 thus permitting the development of Karplus-type relationship^^^ ; the sign was assumed to be positive.24 The magnitude depends on the electronegativity of substituents attached directly, or adjacent, to the coupled carbon atom; increasing electronegativity causes a small decrease, whereas a large decrease is observed on change from a trans to a gauche orientation of the coupled nuclei. A large increase in the coupling constant is found if the orientation of an electronegative substituent attached to the middle carbon atom of the coupling pathway changes from trans to gauche relative to the fluorine atom, even though the relative positions of the coupled nuclei are held constant.24 4J( uC, 'V). Although there are only a few examples of this long-range coupling, dependences on orientation may be detected. Observable values could only be obtained for equatorially disposed fluorine atoms (except for those in glycosyl fluoride^).^^
-
3. 19F-N.m.r. Spectroscopy a. 19F-Chemical Shifts.-Because the 19F-nucleus shows spectroscopic behavior similar to that of the IH-nucleus (compare Table I) I9Fn.m.r. spectroscopy was used, even at the very beginning of n.m.r. spectroscopy of carbohydrates. I9F-N.m.r. spectroscopy offers some important benefits: the nucleus is at isotopic abundance, the gyromagnetic ratio is high, and the relevant spectroscopic parameters may be readily extracted from the spectra. Importantly, this nucleus is a probe that is very sensitive to changes in the steric and electronic environment.2yIn this way, lyF-n.m.r.spectroscopy must be regarded as a part of (29) L. Phillips and V . Wray, J . Chem. SOC., Perkin Trans. 2, (1972) 223-228.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
79
the “structural-reporter-group concept” originally developed for IHn. m. r. spectroscopy of oligosaccharides.30 The main difference between 19F-n.m.r.and ‘H-n.m.r. spectra is exemplified by the tremendously enlarged range of chemical shifts. This range reflects the presence of nonbonding electrons on fluorine, in general giving rise to low energy n-r* transitions, and thus the large paramagnetic contributions to the nuclear shielding tensor will cause nuclear deshielding, whereas the diamagnetic contributions are rather small The extensive investigations of single groups of fluorinated carbohydrates has not only provided fundamental information for establishing the structures of the fluorinated derivatives but has also shown I9F to be a very sensitive probe and, as Inch pointed out,5 as an “amplifier” for showing conformational distortions and mobility. The chemical shifts of fluorine atoms are dependent on their site, and their orientation with respect to the carbohydrate ring.29Because only empirical correlations have been made between chemical shifts and stereochemistry, these rules can only be applied to compounds that are closely related structurally to those which have been utilized to establish these correlations.I6 Shifts of I9F although at least one order of magnitude greater than the corresponding IH-values, are therefore generally only indicative, for example, of the chemical environment of fluorine within the molecule. l6 Primary and secondary fluorides may be clearly differentiated; primary resonate at higher field than secondary fluorides; glycosyl fluorides resonate at still lower field. Tertiary fluorides and secondary geminal difluorides resonate still further to low field. The fluorine shifts of a-aldohexopyranosyl fluorides, having an axially oriented fluorine atom, are at higher field than those of the corresponding, equatorially oriented p counterpart^,^^-^^ which, in turn, were found to display temperature-dependent Chemical shifts and chemical-shift differences between pairs of anomers in the monodeoxymonofluoro-D-hexopyranose series were observed to be strongly dependent on the stereochemistry of electronegative substituents in the molecule. In consequence, no a priori distinction between anomers can be made on the sole basis of their respective fluorine shifts.23 The use of fluorine shifts as a probe for structural and conformational (30) J. F. G . Vliegenthart, L. Dorland, and H. Van Halbeek, Adu. Carbohydr. Chem. Biochem., 41 (1983) 209-374. (31) J. B . Lambert and F. G . Riddel (Eds.), The Muftinuclear Approach to N.m.r. Spectroscopy, Reidel, Dordrecht, 1983. (32) L. D. Hall and J . F. Manville, Chem. Ind. (London), (1965) 991-993. (33) L. D. Hall and J. F. Manville, Can. J . Chem., 45 (1967) 1299-1303. (34) L. D. Hall and J. F. Manville, Can. J . Chem., 47 (1969) 361-377.
80
RENE CSUK AND BRIGITTE I. GLANZER
parameters therefore remains of limited value. Furthermore, data reported in the literature need to be viewed with caution because of strong and non-negligible solvent- and temperature-effects on the chemical shifts .35 b. 19F-19F Coupling.-In contrast to IH-I9F and I3C-I9F couplings, I9F-l9F couplings may only be used with caution for stereochemical assignment. Geminal 2J ( I9F, 19F)couplings ranging from -240 to 300 Hz for sp3-hybridized carbon atoms, and some 30-40 Hz for sp2, have been reported. Analysis of 3J ( 19F, I9F) couplings revealed that the angular dependence is more complex than for the corresponding ‘H-IH or IH-l9F couplings. trans-Vicinal were assumed to be more sensitive than gauchevicinal couplings.36These couplings are absolutely negative, and range36 between 10 and 20 Hz. The values of 4J (I9F, I9F) may be of different sign, with J (e,e) being absolutely negative, and J @ , a )and J (a,a)being positive.I7 Although the magnitude of coupling depends on the relative orientation of substituents, there is no enlarging effect of an “M” relationship of the coupled nuclei.21 The values of 5J (I9F, 19F)are of variable sign and are presumed to occur by way of through-bond interaction; their stereospecific dependences seem to be rather complex.I0 4. Other Nuclei
There is little known in the carbohydrate field about coupling of fluorine with nuclei other than ‘H, I3C, or 19F.Tronchet and coworkers37investigated the 2H-19Fcoupling in (2)-and (E)-3-deoxy-3-C-(fluoromethylene)1,2: 5,6-di-O-isopropylidene-a-~-ribo-hexofuranose deuterated at the sp2hybridized fluoromethylene group. The 2J ( 2H, I9F) coupling is, in comparison with the corresponding IH-I9F coupling, significantly lessened (12.4 Hz us. 82 Hz), thus limiting its use and potential significance.
111. TABLES 1. Guide to Use of the Tables
All fluorine chemical-shifts given in this compilation have been converted to the 6 scale, with trichlorofluoromethane (Freon-I 1) as refer(35) H. Giinther, NMR-Spektroskopie, G. Thieme Verlag, Stuttgart, 1973. (36) L. D. Hall, R. N . Johnson, J. Adamson, and A. B. Foster, Chem. Commun., (1970) 463-464. (37) J. M. J. Tronchet, D. Schwarzenbach, and F. Barbalat-Rey, Carbohydr. Res., 46 (1976) 9-17.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
8I
TABLEIV Conversion Factors Used Throughout this CompilationB Reference material
Shift (to Freon-11) (in p.p.m.)
Reference material
Shift (to Freon-11) (in p.p.m.)
F2 C~HSSO~F CFCI3 CF2CIi C6HsCF3 CFC12-CFCI2 CF$Z02CHX
+422.9 +65.5
CF3C02H CFICCIX CF3COCF3 CFC(OH)2CFj
-78.5 -82.2 -84.6 -92.7 -113.1 - 120.0 - 162.9
0.0
-6.9 -63.9 -67.3 -74.2
FC6H4F-p C6F6
ence, and with positive shifts to high frequency of the reference, using the conversion factors shown in Table IV. Because some authors omit indication of sign or standards, or change conventions, some errors may be present in the tables. Tables V-LVII detail ‘H and I9F shift and coupling information, and Tables LVIII to LXXI incorporate the 13C-n.m.r.data. The data within this compilation are arranged according to the following outline: hexoses prior to pentoses, followed by anhydro sugars, sugar acids and lactones, amino sugars (and their synthetic, N-containing precursors), mono-, di-, and tri-deoxy sugars, branched derivatives, ketoses, polyfluorinated monosaccharides, and, finally, difluorinated amino sugars. Within this compilation, and even within each table, pyranoid derivatives are listed prior to their furanoid counterparts, hexoses prior to pentoses, functionalized prior to deoxy compounds; the arrangement within each “sub-table” is made alphabetically. The tables contain nearly all of the n.m.r. information currently available in the literature. Although there are more fluorinated monosaccharides known, for many of them no n.m.r. data have been reported so far. Throughout the Tables, “S” stands for “solvent”: A for hexadeuterioacetone, B for hexadeuteriobenzene, C for deuteriochloroform, D for deuterium oxide, F for liquid hydrogen fluoride, H for water, M for tetradeuteriomethanol, N for dichlorodideuteriomethane, and s for hexadeuteriodimethyl sulfoxide.
(38) V. Wray, Annu. Rep. NMR Specfrosc., 10B (1980) 5.
RENE CSUK AND BRIGITTE I. GLANZER
82
TABLEV 'H- and I9F-N.m.r. Data for Hexopyranosyl Fluorides
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
Jz,~
53.4
54.5
55.6
55.6
56,6
JF,l
JF,Z
JFJ
JF,4
JFJ
Jv.6
JF.6'
6F
S
References
2,3,4,6-Tetra-0-acetyl-o-allopyranosyl fluoride a anomer 5.55 4.79 3.2 3.2 53.5 26.0 p anomer 5.41 5.07 7.3 2.8 52.7 12.0
5.32 3.0
5.12 10.2
4.00 4.6
5.38 2.8
5.05 9.5
3.96
4.20
- 145.5
17"
4.20
- 146.3
17"
2.3
2,3,4,6-Tetra-0-acetyl-~-gdactopyranosy~ fluoride a anomer 5.82 5.27 5.50 2.8 10.0 b2.3 53.0 21.8 p anomer 5.55 5.09 5.06 7.0 10.3 3.4 52.0 12.6 D-Glucopyranosylfluoride a anomer 5.66 3.0 53.2 27.2 p anomer 5.31 6.66 52.0 12.0 2,3,4,6-tetra-O-acetyla anomer 5.74 4.94 5.48 2.7 10.0 9.5 52.8 23.8 p anomer 5.40 5.12 5.20 6.6 9.0 9.0 52.5 12.0
5.55
1.8
4.34 5.1
5.41 2.0
3.69 b4.9
4.18 7.3
%.0
4.06 10.8 4.15 b11.4
-150.1
17,32 a
-141.9
17,32 u
- 146.2
23
-139.1
23
5.14 9.7
4.18 2.0
4.28 4.2
4.12 12.7
- 149.9
14,15, 17,32,33, 39,40"
5.20 9.4
3.92 3.0
4.30 5.0
4.22 12.8
- 137.8
14,15, 17,32,33, 40"
3.60
- 147.5
14,15, 17
2,3-di-O-acetyl-4,6-O-benzylidenea anomer
5.65 3.0 53.0
4.88 9.8 24.6
5.43 9.4
4.30
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
83
TABLEV (continued) Compound H-1 H-2 51.2
JFJ
JF,Z
H-3
H-4
H-5
H-6
H-6‘
J3.4
J4.5
55.6
55.6’
J6,6’
JFS
JF,~
JFS
JF,~
JF,6‘
&F
S
References
p anomer
5.55 6.2 53.4
5.02 5.34 4.5 7.8 8.8 11.6 3,4,6-tri-O-acetyl-2-O-methyla anomer
3.60
-138.1
2.5
A
14,15, 17
C
41‘
C
41d
24.4
p anomer 6.4
2,3,4,6-tetra-O-benzoyla anomer
6.19 2.8 53.2
5.64 6.23 5.99 9.6 9.6 9.5 23.7 p anomer 5.26 5.75 6.23 5.84 5.7 8.6 8.6 8.6 51.5 10.3 3,4,6-tri-O-benzoyl-2-O-methyla anomer 5.84 3.65 5.95 5.63 2.7 9.6 9.6 9.6 . 52.0 24.3 p anomer 5.48 3.62 5.70 5.61 6.0 7.8 8.5 8.5 52.4 10.4 2,4,6-tri-O-benzoyl-3-O-methyl(Y anomer 5.70 5.22 4.00 5.63 2.7 9.5 9.5 9.5 53.4 24.3 p anomer 5.63 5.45 3.90 5.60 4.5 6.0 7.5 7.5 51.2 7.5
4.80 4.5
4.74 2.6
5.58 12.2
-148.6
A
17,32
3.87 5.0
4.62 3.6
4.40 11.9
-136.4
B
17,32
4.53 ‘4.3
4.64 ‘3.7
4.42 ‘12.6
-149.9
C
17,32
4.25 5.0
4.65 3.6
4.45 12.3
-135.2
4.32
4.55
4.32
-148.8
Y
C
17,32 (I
B
17,32 (I
4.35 5.0
4.62 5.0
4.55 12.0
-131.8
C
17,32 (1
(continued)
TABLEV (continued) Compound H-1 H-2 Jis J2.3 JFJ
J F ~
H-3
H-4
€I-5
H-6
H-6‘
53.4
J4,s
554
Js.6,
J6.6‘
JFJ
JFC
JFS
JF,~
JF,~’
2,3-di-O-benzoy1-4,6-di-O-methyla anomer 4.06 3.70 3.76 5.9 5.19 5.91 10.0 10.2 9.0 2.8 53.5 23.7 p anomer 5.58 5.2-5.9 3.6 6.0 53.0 6.0 2,3,4,6-tetra-O-benzyl-a5.55 2.68 53.2 25.4 2,3,4,6-tetra-O-methyla anomer 5.67 3.20 3.55 3.28 3.60 3.78 2.7 9.6 10.2 10.2 2.7 2.7 53.5 25.0 p anomer 5.11 6.5 53.0 D - M Q I I I I O ~ ~ I Ifluoride OS~I 2,3,4,6-tetra-O-acetyla anomer 5.66 5.26 5.34 4.18 1.3 10.0 10.0 f4.5 r3.6 48.5 1.5 p anomer 5.45 5.25 5.04 5.04 3.82 4.38 1.9 2.2 5.7 4.7 5.7 5.6 51.2 13.9 3,4,6-tri-O-acetyl-2-0-methyl-a2.1
6F
S
References
3.70
C
42
3.9
C
42
-149.0
C
43
-149.9
C
44
-138.7
C
44
-138.2
A
17,32, 40
-142.0
C
28,39, 32
c
41
3.60
f13.0 4.22 11.8
8
0.8
2,3,4,6-tetra-0-benzoyl-a5.84 5.86 5.90 6.22 4.77 4.61 1.1 9.5 e9.5 ‘2.0 ‘4.9 c48.5 ‘1.0 2,3-di-O-benzoy1-4,6-di-O-methyla anomer 5.71 5.69 5.60 3.6 1.6 49.0 1.6
4.49 ‘12.5
4.15
-138.7
C
17,32
C
42
(continued)
85
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES TABLEV (continued)
p anorner 5.75 5.80 5.60 3.7 1.5 3.4 6.9 51.6 12.9 2-O-benzoyl-4,6-di-O-methyl-a5.67 5.47 4.16 3.6 2.0 3.5 8.7 0.5 49.5
3-0-benzoyl-4,6-di-O-methyl-/3-
5.56 1.8 52.8
4.28 3.6 14.6
5.28 6.4
3.5
-
4.1
C
42
-
3.90
C
42
-
3.90
C
42
Ref. 17 reported chemical shifts and coupling constants for solvents A, B, and C. Coupling constant measured in A. J ( F, OMe) = 1.0 Hz.d J (F,OMe) = 1.4 Hz. Coupling constant measured in B. f Coupling constant measured in C. g J (F, OMe) = 0.55 Hz.
(39) C. J. S. Van Rijn, J. D. M. Herscheid, G. W. M. Visser, and A. Hoekstra, Znt. J. Appl. Radiat. Isot., 36 (1985) 111-115. (40)L. D. Hail and J. F. Manville, Chem. Commun., (1968) 37-38. (41) A. B. Foster, R. Hems, J. H. Westwood, and L. D. Hall, Carbohydr. Res., 23 (1972) 316-3 18. (42) c. Pedersen and S. Refn, Acta Chem. Scand., Ser. B, 32 (1978) 687-689. (43) M. Hayashi, S. Hashimoto, and R. Noyori, C h m . Lett., (1984) 1747-1750. (44) G. L. Trainor, J. Carbohydr. Chem., 4 (1985) 545-563.
TABLEVI lH- and '9F-N.m.r. Data for 2-Deoxy-2-Buoro-hexopyranoses and hexopyranosides
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JI,Z
I23
53.4
JW
J5.6
JW
JW
JFJ
JF,Z
IF3
J F ~
JFJ
Jp.6
JFC,
2-Deoxy-2-Buoro-~-g~a~opyranose a anomer 4.44 4.0 10.5 3.5 0.5 50.5 13.3 2.8 /3 anomer 5.06 7.3 7.5 3.2 3.0 51.5 14.5 2.8
SF
S
-203.1
D
References
45,46, 47 a
-202.9
D
45,46, 47 b
(continued)
RENfi CSUK AND BRIGITTE I. GLANZER
86
TABLEVI (continued) Compound H-1 H-2 Ji,z Jzs JF.~
JF,Z
€5-3
H-4
H-5
H-6
H-6'
J3.4
543
55.6
Js,6*
16.6'
JF.~
Jp.4
JFJ
JFC
JF,~'
1,3,4,6-tetra-O-acetyla anomer 6.48 4.90 5.40 5.31 4.32 10.0 3.@ 3.5 4.0 49.0 11.0 3.5 p anomer 5.10 4.41 5.10 5.34 8.0 9.6 3.5 0.0 4.0 51.1 13.1 2.1 2-Deoxy-2-fluoro-~~g~a~opyranoside methyl p4.65 4.38 9.0 9.0 3.0 52.0 methyl 3,4-O-isopropylidene-6-O-trityl-p4.3 4.24 3.41 1.4 1.45 2.0 47.6 trifluoromethyl 3,4,6-tri-O-acetyl-a5.15 4.17 5.32 5.46 4.35 1.o 3.1 10.5 3.5 0.5 48.5 11.0 3.5 2-Deoxy-2-fluoro-~-glucopyranose a anomer 5.39 4.36 3.32 3.66 9.5 0.5 48.9 14.5 p anomer 4.85 4.05 3.32 1.8 8.8 2.5 50.0 14.5 1,3,4,6-tetra-O-acetyla anomer 6.46 4.64 5.56 5.08 4.03 4.0 9.6 9.6 9.6 2.3 0.5 48.5 12.0 p anomer 5.64 4.33 5.23 4.90 3.11 8.1 8.8 9.6 9.1 4.1 3.0 51.0 14.5 2-Deoxy-2-fluoro-n-glucopyranoside methyl 4,6-di-O-acetyl-3-O-benzyl-p4.42 4.39 3.49-4.34 5.05 3.49 1.7 1.7 9.1 9.1 1.7 52.0
4.10
4.00
References
6F
S
-201.1
c
48,49, 50
-208.1
C
45
-203.9
D
51
C
52
4.33
4.03
-211.0
C
45,46, 5334
4.08
-194.8
D
12,23,24, 47,55,56, 57,58,d
4.08
-194.6
D
23,24,47, 55,56,57, 58,'
4.00 12.5
4.22 12.5
-202.9
C
39,48,49, 50,56,51
4.30 1.6
3.98 12.4
-201.4
C
39,56,57, 58,59
-
4.34
C
57
4.03
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
87
TABLEVI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.2
J23
J3.4
34.5
Js.6
55.6'
J6.6'
JFJ
JF,~
JFJ
JFA
JF,S
JF,~
JF,~
methyl 3-0-acetyl-4,6-0-benzylidene-p4.55 4.28 5.45 4.39 3.49 7.6 8.8 9.9 4. I 1.5 49.0 methyl 4,6-0-benzylidene-3-O-methyl-p 4.49 4.25 3.40-3.88 4.38 3.40 7.9 7.9 10.2 4.5 2.7 51.2 methyl 3-0-benzyl-4,6-0-benzylidene-p4.49 4.34 3.75 4.38 3.40 7.8 7.8 8.0 4.6 2.W 51.0 15.0 phenyl 3,4,6-tri-O-acetyl-P5.13 4.57 5.42 5.10 3.85 4.14 7.7 8.6 9.1 9.7 5.2 2.7 3.2 50.0 14.1 trifluoromethyl 3,4,6-tri-O-acetyl-a3.9 0.5
9.7
9.4 11.5
6F
S
References
3.89
C
57
3.88
C
57.60
3.94
C
57,61
4.31 12.0
C
62
-195.4
C
58
-200.8
D
23,24,47, 55,56,58, 63,64,8
-219.3
D
23,24,47, 55,5633, 63,64,*
9.4
2-Deoxy-2-fluoro-o-mannopyra~1ose
a anomer 5.37 4.77 1.95 2.2 7.6 49.1 30.0 p anomer 4.99 4.81 1.0 2.44 20.5 51.3 32.0 1,3,4,6-tetra-O-acetyla anomer 6.09 4.59 5.02 1.9 2.4 10.2 6.3 48.9 27.2 /3 anomer 5.07 5.81 4.87 1.0 2.4 10.0 19.0 51.2 27.0
5.18 9.8
3.88 4.7
4.18 2.2
3.91 12.6
-201.2
C
39,56, 58,63
5.37 10.0
3.81 4.8
4.30 2.3
4.16 12.5
-220.2
C
39,49, 5036, 58,63
3.4
-
4.34
C
63
1,4,6-tri-O-acetyl-3-O-methyl-
a anomer 6.28 4.80 2.0 2.0 7.0 49.0
3.4-4.34 10.0
5.32 10.0
(continued)
RENC CSUK AND BRIGITTE I. GLANZER
88
TABLEVI (continued) Compound H-1 H-2
Jiz
Jw
JFJ
J F ~
H-3
H4
H-5
H-6
H-6’
J3.4
J4.5
15.6
J5,v
J6.6,
JF3
J17.4
JFJ
JF,~
JFC’
p anomer 5.74 4.93 5.26 1.0 2.0 10.0 10.0 19.0 52.0 Methyl 2-deo~2-Buoro-~-maopyraooside 3,4,6-tri-O-acetyI-p4.52 4.82 4.99 5.36 3.54 1.0 2.5 9.9 9.9 17.6 51.0 27.0 4.90 2.0 52.0
S
References
C
63
C
63
C
63
C
63
C
63
5.54 10.0 28.0
C
61
C
61
C
63
4,6,di-O-acetyl-3-O-rnethyl-/3-
4.44 1.0 18.0
&F
3.2-3.7 10.0
5.24 10.0 4.39 4.9
3.38
4.36 6.0
3.24
4.32
4.36
3.2-3.7
3-0-acetyl-4,6-O-benzyIidene-P-
4.57 4.92 5.07 1.0 2.7 10.3 20.0 50.0 25.8 4,6-O-benzylidene-p4.42 4.78 3.24-4.0 1.0 3.0 10.0 20.0 50.0
-
-
4.18
4.0
3-0-benzoyl-4,6-0-benzyIidenea anomer
4.94 3.0 8.0
3.0
4.62 0.0 19.0
5.02 2.5 51.0
5.34 10.0 26.0
4.40 1.0 19.0
4.78 3.0 51.0
3.24
p anomer
3-0-benzyl-4,6-O-benzylidene-p-
-
4.44
Tritluoromethyl3,4,6-~-0~ecetyl-2-deoxy.2-fluoro-~~-mannopyranoeide 1.0 2.5 9.7 9.0 16.0 25.0 ~-Deoxy.~-flnoro-D-t~opyrnnose a anomer
12.2
44.0
-203.4
C
58
D
47
34.2 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
89
TABLEVI (continued)
p anomer 19.7 51.2 32.9 2-Deoxy-2-fluoro-~-tdopyranoride tritluoromethyl3,4,6-tri-O-acetyl-p5.17 4.67 4.99 5.25 4.23 1.0 3.0 3.5 1 .o 16.5 51.0 29.0
-
3.97
-223.5
D
47
-220.0
c
45
Ref. 47 reported a chemical shift of -208.8 a Ref. 47 reported a chemical shift of -208.9 p.p.m. p.p.m. Ref. 48 reported acoupling of 1.2 Hz. Ref. 47 reported a chemical shift of -200.6 p.p.m. Ref. 47 reported a chemical shift of -200.4 p.p.m.fRef. 61 reported a coupling of 4.0 Hz.g Ref. 47 reported a chemical shift of -206.0 p . p m * Ref. 47 reported a chemical shift of -224.5 p.p.m.
(45) J. Adamson and D. M. Marcus, Carbohydr. Res., 22 (1972)257-264.
(46)J. Adamson and D. M. Marcus, Carbohydr. Res., 13 (1970)314-316. (47) M. Diksic and D. Jolly, J . Carbohydr. Chem., 4 (1985)265-271. (48) M. J. Adam, B. D. Pate, J. R. Nesser, and L. D. Hall, Carbohydr. Res., 124 (1983) 215-224. (49) B. I. Glanzer and K. Dax, Eur. Symp. Carbohydr., 3rd, Grenoble, 1985,B.l-24. (50) B. I. Glanzer, Diplomarbeit, Techn. Univ. Graz, 1985. (51) Y. Ittah and C. P. J. Glaudemans, Carbohydr. Res., 95 (1981) 189-194. (52) T. Haradahira, M. Maeda, Y. Yano, and M. Kojima, Chem. Pharm. Bull., 32 (1984) 3317-3319. (53) P. W.Kent, R. A. Dwek, and N. F. Taylor, Tetrahedron, 27 (1971)3887-3891. (54) R.A. Dwek, P. W. Kent, P. T. Kirby, and A. S. Harrison, Tetrahedron Lett., (1970) 2987-2990. (55) G. T. Bida, N. Satyamurthy, and J. R. Barrio, J. Nucl. Med., 25 (1984)1327-1334. (56) G. K. Mulholland and R. E. Ehrenkaufer, J. Org. Chern., 51 (1986) 1482-1489. (57) T. Haradahira, M. Maeda, Y. Kai, H. Omae, and M. Kojima, Chem. Pharm. Bull., 33 (1985)165-172. (58) J. Adamson, A. B. Foster, L. D. Hall, R. N. Johnson, and R. H. Hesse, Carbohydr. Res., 15 (1970)351-359. (59) S. R. Thomas, J. L. Ackerman, J. R. Goebel, M. Davis, J. G. Kereiakes, and Y. Y. Lin, Magn. Reson. Imaging, l(1982) 11-21. (60)S. Levy, E. Livni, D. Elmaleh, and W. Curatolo, J. Chem. Soc., Chem. Commun., (1982)972-973. (61) A. Olesker, A. Dessinges, T. T. Thang, and G. Lukacs, C. R . Acad. Sci. Ser. 2 (Paris), 295 (1982)575-577. (62) J. PacBk, Z.KollnerovB, and M. Cernf, Collect. Czech. Chem. Commun., 44 (1979) 933-941. (63) T.Haradahira, M. Maeda, H. Omae, Y. Yano, and M. Kojima, Chern. Pharm. Bull., 32 (1984)4758-4766. (64)T. Ogawa and Y. Takahashi, J. Carbohydr. Chem., 2 (1983)461-467.
RENI? CSUK AND BRIGITTE I. GLANZER
90
TABLEVII 'H- and '9F-N.m.r. Data for 3-Deoxy-3-fluoro-hexopyr~noses and -hexopyranosides Compound H-1 H-2
H-3
Jw
52.3
J3-4
JF.1
JFZ
JFS
H-4 JF,~
H-5 H-6
H-6'
Js.6
J5,6*
JFJ
J F , ~ JF,~'
References
&F
S
-217.2
A
65
-217.4
C
65
-217.4
A
65
-217.4
A
65,66
-204.3
C
67,68
-200.7
C
67,68
C
69
C
69
D
12,23, 53,70, 71
J6,6'
Methyl 3-deoxy-3-fluoro-~-~opyranoside p anomer 4.48 3.40 4.86 8.0 2.0 2.0 29.0 53.0 4,6-O-isopropylidene-p4.53 3.65 4.97 3.53 8.0 28.0 54.0 27.0 6-O-pivaloyl-p3.42 4.92 3.67 3.86 4.21 4.44 8.0 2.0 6.0 2.0 11.0 30.0 53.0 28.0 6-0-trit yl-/34.62 3.55 4.94 3.80 3.87 3.33 3.50 8.0 1.5 8.0 5.4 2.2 10.0 1.5 53.0 28.0 ~-Deoxy-~-fluoro-~-gPactopyranose 1,2,4,6-tetra-O-acety1a anomer 6.41 5.40 4.86 5.69 4.4 3.95 3.6 10.0 3.6 1.0 4.8 11.4 47.5 6.4 p anomer 5.64 5.38 4.70 5.59 4.24 3.92 8.1 9.5 3.8 0.5 11.5 47.4 5.6 3-Deoxy-3-fluoro-~-gPactopyranos~de methyl 2,4-di-O-benzoyl-6-O-(bromoacetyl)a anomer 5.26 5.54 5.22 5.91 4.25 4.43 4.0 10.0 4.0 1.0 4.0 10.0 48.5 5.5 p anomer 4.60 5.67 4.93 5.87 4.07 4.36 4.36 10.0 4.0 1.0 6.0 6.0 8.0 12.0 47.0 5.0 ~-~eoxy-~-fluoro-~-~ucopyranose a anomer 5.35 3.6 3.9 12.0 53.0 13.6
-195.4
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
91
TABLEVII (continued) ~
Compoond H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.1
JZJ
J3.4
J~J
Js.6
J5.6,
56.6,
JFJ
JF,Z
JFJ
JFA
JFJ
J F , ~ JF.~'
@ anomer 4.75 7.5 0.5 13.0 52.0 6-phosphate a anorner
3.0
12.0
p anomer
52.0
-190.5
3-Deoxy-3-fluoro-~-idopyranose a anomer
3.0
9.0
51.0
46.0
D
12,23, 53,70, 71
D
66
D
66
3.9
-200.4
C
4.09 12.5
-196.2
C
20,53
-194.0
D
53
-194.0
C
53
-198.6
C
20
-197.0
D
53,71
-189.3
D
72
-190.8
D
72
15.0 57.5 15.0 methyl 2-O-acetyl-4,6-O-benzylidene-a4.07 5.39 4.53 3.42 2.99 4.08 3.41 7.5 9.3 9.0 10.0 4.7 9.4 10.6 14.1 53.0 15.1 1.5 2.0 Methyl 3-deoxy-3-8uoro-a-~-gulopyranoside
14.0
References
12.0
benzyl 2,4 ,btri-O-acetyl-P-
p anomer
S
13.0
0.5 13.0 51.0 13.0 1,2,4,6-tetra-O-acetyla anomer 6.31 4.75 4.3 3.2 9.4 9.4 4.0 12.5 52.0 12.5 @ anomer 5.65 5.23 4.60 5.25 3.75 4.29 8.3 8.9 9.2 4.3 2.5 10.0 51.3 12.8 12.8 1.1 1.5 3-Deoxy-3-fluoro-~-~ocopyr~nocl~de benzyl p-
3.0
SF
20
14.0
9.0
3.0 (continued)
RENk CSUK AND BRIGITTE I. GLANZER
92
TABLEVII (continued) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JIJ
J23
J3,4
J4.s
Js,6
Js.6,
J6,6'
JF,I
JF,Z
Jp.3
JF,~
JF,S
JF,~
Jp.6'
~Deoxy-3-fluoro.~-mannopyranose (I anomer 5.23 4.19 4.75 3.62 1.9 3.5 9.4 5.1 7.1 48.6 /3 anomer 4.91 4.19 4.59 3.62 1.1 3.5 9.4 10.0 5.9 2.4 2.1 7.4 48.0 1.2 1,2,4,6-tetra-O-acetyI-a6.14 5.36 4.91 5.46 3.97 4.28 2.0 3.8 9.6 10.1 5.0 2.5 4.7 48.0 11.4 5.8 1.0 0.0
SF
S
References
4.03
D
73
4.03
D
73
4.13 12.5 1.5
C
73
P. J. Card and G. S. Reddy, J . Org. Chem., 48 (1983)4734-4743. D. G.Drueckhammer and C. H. Wong, J . Org. Chem., 50 (1985)5912-5913. J. S.Brimacombe, A. B. Foster, R. Hems, J. H. Westwood, and L. D. Hall, Can. J . Chem., 48 (1970)3946-3952. J. S. Brimacombe, A. B. Foster, R. Hems, and L. D. Hall, Curbohydr. Res., 8 (1968) 249-250. P. KovBe and C. P. J. Glaudemans, J . Curbohydr. Chem., 4 (1985)613-626. N. F. Taylor, B. Hunt, P. W. Kent, and R. A. Dwek, Carbohydr. Res., 22 (1972) 467-469. P. W. Kent, R. A. Dwek, and N. F. Taylor, Biochem. J . , 121 (1971)1OP-llp. A. B. Foster, R. Hems, J. H. Westwood, and J. S. Brimacombe, Curbohydr. Res., 25 (1972)217-227. M . Cernf, J. DoleMovB, J. MBcovB, J. PacBk, T. Trnka, and M. BudeSlnskf, Collect. Czech. Chem. Commun., 48 (1983)2693-2700. TABLEVIII IH- and W-N.m.r. Data for 4-Deoxy-4-fluoro-hexopyranoses and -hexopyranosides
4-DeoKy.Qfluoro-D-gnladopyranose
1,2,3,6-tetra-O-acetyI-p-
8.0 0.8
10.0
2.5 26.5
1.0
-217.4 25.0
1.0
C
19
1.0 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
93
TABLEVIII (continued) ~
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JIJ
JZJ
J3.4
J4.5
55.6
55.6'
J6.6'
JFJ
JF,Z
JFJ
JFI
JFJ
JP,~
J F , ~
Methyl 4-deoxy-4-8uoro-o-gelPctopyranoside 2,3,6-tri-O-acetyl-a5.01 5.20 5.28 4.92 4.06 4.23 3.50 10.5 2.5 2.5 6.5 7.0 3.7 25.5 51.0 29.0 3.7 2,3,6-tri-O-benzoyl-p8.0 0.5
9.8
2.8 25.0
1.2 50.0
4.31 11.5
51.0
49,50 65,74
B
75
C
51
D
76
-219.9
A
65,77
-194.3
D
12,23,78
-195.3
D
12,23
C
12,79
A-M
65,80
27.0 3.86
3.74 12.0
3.81 4.85 3.91 2.50 6.5 29.0 51.0 30.0 ~Deoxy48uoro-o-~uropyraoose a anomer 5.56 3.5 3.5 15.0 49.0 4.5 p anomer 5.01 7.8 0.0 16.0 49.5 4.5 1,2,3,6-tetra-O-acetyI-p-
3.28 6.5
3.34 9.0
8.1
References
C
-219.7
-217.3
3.44
6-0-trityl-a4.41 3.68 3.50"
4.73
S
25.0
6-0-benzoy1-2,3-di-O-benzyl-/327.0 2,3-di-O-benzyl-p4.30 3.69 3.49
SF
3.0
2.0
3.0
2.0
9.5
8.8 10.0 2.5 4.4 12.4 14.5 49.5 2.6 1.6 1.5 Methyl 4-deoxy-4-8uoro-~-~ucopyr~oside a anomer 4.47 3.64 4.0 3.15 3.15 3.5 9.0 9.0 9.0 50.0 3.5 16.5 2,3,6-tri-O-acetyl-a4.65 3.42 3.7 5.70 4.10-4.60 9.5 9.5 3.8
-198.0
B
80
(conrinued)
RENfi CSUK AND BRIGITTE I. GLANZER
94
TABLEVIII (continued) Compound
S
H-1
H-2
H-3
H-4
H-5
H-6
H-6’
J1.z
JZJ
53.4
J4s
Js,6
Js.6,
J6.6’
JFJ
JF,Z
JFS
JF,~
JFJ
Jp.6
J17.6’
4.33
4.67
4.67 12.8
-197.6
C
27
3.89 4.34 4.29 3.21 3.65 4.81 4.7 9.9 2.7 8.4 3.6 9.5 15.8 50.2 4.6 1.9 3.3 0.7 2,3-di-O-rnethyl-a4.76 4.30 3.8 8.8 8.8 3.8 15.0 49.5 Methyl 4-deoxy-4-8uoro-~-tdopyrnnoside Q anomer 4.74 4.77
4.23 12.0 1.3
-196.1
C
12,78
C
78
-217.1
A
65
-215.0
C
65
2,3,6-tri-O-benzoyl-a5.22 5.18 6.12 4.77 3.5 9.0 9.1 10.0 14.7 51.3
6-O-acetyl-2,3-di-O-methyl-a-
6-O-trityl-a4.79
6F
References
b
49.0 4.85 49.0
Ref. 77 reported a coupling of 5.34 Hz. J (F,OMe) = 0.8 Hz.
(74) D. M. Marcus and J. H. Westwood, Curbohydr. Res., 17 (1971) 269-274. (75) A. Maradufu and A. S . Perlin, Curbohydr. Res., 32 (1974) 261-277. (76) T. C. Wong, V. Rutar, J. S. Wang, M. S. Feather, and P. Kov612,J . Org. Chem., 49 (1984) 4358-4363. (77) C. W. Somawardhana and E. G. Brunngraber, Curbohydr. Res., 121 (1983) 51-60. (78) A. B. Foster, R. Hems, and J. H. Westwood, Curbohydr. Res., 15 (1970) 41-49. (79) A. D. Barford, A. B. Foster, J. H. Westwood, and L. D. Hall, Curbohydr. Res., 11 (1%9) 287-288. (80) D. P. Lopes and N. F. Taylor, Curbohydr. Res., 73 (1979) 125-134.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
95
TABLEIX 'H- and WF-N.m.r. Data for bDeoxy-6-fluoro-hexopyranoses and -hexopyranosides Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1J
JZJ
J3.4
J4.5
Js,6
-fs,a.
16.6,
JFJ
JFJ
JFS
Jp.4
JFJ
JF,6
JF.6'
S
References
-229.0 D
81
--229.2 D
81
-230.6 C
81
SF
6-Deoxy-6-Buoro-~-galPctopyranose a! anomer
p anomer
I ,2,3,4-tetra-O-acetyl-a-
15.8
18.5
46.7
46.6
46.6
11.8 48.0 48.0 1,2:3,4-di-O-isopropylidene-a5.55 4.35 4.63 4.27 4.08 4.54 4.58 5.0 2.50 7.90 2.00 6.90 5.2 9.5 1.O 1 .o 13.5 46.2 47.1 Methyl 6-deoxy-6-fluoro-~-gala~opyranoside a! anomer 16.9
46.4
-229.5 C
4431,82
-230.0 D
53,71,81
46.4
2,3,4-tri-O-acetyl-a!6-Deoxy-6-fluoro-~-glucopyranose a anomer 3.51 5.26 3.55 3.75 3.98 3.8 9.8 8.8 9.8 3.6 0.0 28.6 0.7 p anomer 3.53 4.69 3.27 3.50 3.64 7.8 9.2 2.4 26.0 1,2,3,4-tetra-O-acetyIa! anomer 6.33 5.06 5.49 5.13 4.10 3.8 10.2 9.4 10.2 23.1 p anomer 5.74 5.0 5.38 3.84 7.5 9.6 2.3 21.9
-229.0 C
53
4.75 4.66 -231.4 D 1.9 10.8 46.7 48.0
12,23,81,83
4.71 4.70 -230.6 D 3.4 10.6 47.4 47.5
12,23,83
4.44 46.9
4.44 -233.7 C
84
46.9
4.49 4.43 4.2 10.7 47.0 46.8
-233.5 C
84,85,86 (continued)
TABLEIX (continued) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
115
JZJ
J3,4
J4.s
Js,6
Js,6*
166'
JF,~
JF,Z
JFJ
JF,~
J F ~
JFC
JFC.
6-Deoxy-6-tluoro-~-gncopyranoside methyl a anomer
26.2
48.0
48.0
5.0 24.4
4.61 2.0 48.0
4.68 10.0 48.0
/3 anomer
4.23 8.0
2,3,4-tri-O-benzyl-a4.4-4.7 3.55 4.01 9.3
3.55 10.0
3.13
4.4-4.7
References
6F
S
-234.5
C
27,7Ia
-233.1
A
65,1Ib
-234.5
C
44
-233.5
A
65
28.5
41.5
3.86 5.0 24.0
2.0 48.0
48.0
3.83 4.5 21.0
4.52 2.0 48.0
4.68 10.0 48.0
-236.6
A
65
3.74 4.63 5.0 2.0 24.0 48.0 Methyl 6-deoxy-6-~uoro-~-maopyraaoside a anomer
4.70 10.0 48.0
-233.0
A
65
-232.1
A
65
p-nitrophenyl p5.21 8,O phenyl a anomer 5.51 3.58 3.5 10.0
10.0
3.41 9.0
p anomer 5.03 8.0
3.90 10.0
10.0
2,3-O-isopropylidene-a4.87 2,3-di-O-methyl-a4.84 3.63 1.5
3.84
47.5
25.5
49.0
49.0
4.61 2.0 48.0
4.68 10.0 48.0
-235.0
C
65
4.0 3.12
4.66
4.66
-233.6
C
65
22.0
48.0
48.0
a Ref. 77 reported a chemical shift of -219.4 p.p.m. * Ref. 77 reported a chemical shift of -193.5 p.p.m.
(81) L. Evelyn and L. D. Hall,Curbohydr. Res., 47 (1976) 285-297. (82) S. Colonna, A. Re, G. Gelbard, and E. Cesarotti, J . Chem. Soc., Perkin Trans. 1 , (1979) 2248-2252.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
97
A. De Bruyn, M. Anteunis, G. Aerts, and C. K. De Bruyne, Acta Cienc. Ind., 4 (1978) 103-107. E. M. Bessell, A. B. Foster, J. H. Westwood, L. D. Hall, and R. N. Johnson, Carbohydr. Res., 19 (1971) 39-48. M. Sharma and W . Korytnyk, Tetrahedron Lett., (1977) 573-576. M. G. Ambrose and R. W. Binkley, J . Org. Chem., 48 (1983) 674-677.
TABLEX IH- and '9F-N.m.r. Data for Hexofuranosyl Fluorides
D-Gdactofuranosyl fluoride 2,3,5,6-tetra-O-acetyla anomer 5.6 3.3 65.0 19.0 6.5 @ anomer 5.74 5.23 5.08 4.49 0.0 1.4 4.5 4.5 58.0 7.3 1.9 2,3,5,6-tetra-O-benzoyl-P6.04 5.67 5.75 4.96 4.0 5.0 59.0 6.5 1.5 D-GIUCO~IU~OSY~ fluoride 2,3,5,6-tetra-O-acetyla anomer 5.99 5.64 5.56 4.60 3.9 3.0 5.2 8.3 60.8 14.4 1.O p anomer 5.70 5.17 5.47 4.65 0.0 0.0 5.1 9.4 60.3 4.4 5.7 2,3,5,6-tetra-O-benzoyla anomer 6.22 5.54 6.22 5.15 3.7 5.0 6.0 8.6 60.8 16.5 1.O p anomer 5.99 5.64 6.03 5.19 0.0 0.0 5.2 9.0 60.0 4.4 5.2
4.20 12.0
-122.6
C
87
-126.4
C
87
5.42 4.6
4.35 6.8
6.14 4.5
4.7-4.85 7.0
-123.5
C
87
5.28 2.5
4.56 5.5
4.13 12.4
-138.2
C
88
5.33 2.4
4.63 4.6
4.20 12.5
-119.1
C
88
5.84 2.6
4.97 5.1
4.67 12.3
-136.0
C
88
5.88 2.5
5.00 4.6
4.78 12.3
-118.8
C
88
(continued)
98
RENfi CSUK AND BRIGITTE I. GLANZER TABLEX (continued)
D - M P ~ ~ o ~ fluoride o s ~ I 2,3:5,6-di-O-acetoxonium6.12 6.15 6.34 5.96 5.08 5.20-5.50 0.0 6.5 3.0 6.0 8.5 8.0 56.0 5.0 6.0 2,3,5,6-tetra-O-acetyla anomer 5.81 5.43 5.66 4.60 4.15 5.33 4.60 12.5 2.5 5.6 2.0 5.2 4.8 8.5 64.0 14.0 2.0 p anomer 5.80 5.07 5.70 4.47 4.21 5.46 4.62 3.8 5.8 5.1 9.8 12.5 2.6 4.5 65.8 22.4 7.6 2,3:5,6-di-O-benzoxonium5.90 5.4 6.52 6.50 6.77 6.50 0.0 6.5 3.0 6.0 8.5 55.0 5.0 2,3,5,6-tetra-O-benzoyl-a6.05 5.85 6.19 5.12 5.96 5.04 4.70 0.8 5.4 6.0 8.2 2.5 5.1 12.5 59.9 9.0 2.4 2,3:5,6-di-O-isopropylidenea anomer 4.40 4.11 4.06 5.69 4.77 4.85 4.16 0.0 5.9 3.6 6.1 4.5 7.7 8.8 59.5 6.1 p anomer 5.51 4.71 4.84 4.19 4.47 4.09 3.7 6.2 5.4 7.9 5.5 5.5 66.5 15.3 5.4 2,3,5,6-TebP-0-benzoyl-~~-talofuranosyl fluoride 6.00 5.70 4.99 6.00 4.83 4.73 0.0 3.6 6.0 4.0 6.0 12.0 61.0 2.3 4.5 7.5
F
88
-122.8
C
88
-127.3
C
88
F
88
-121.6
C
88
-130.0
C
89,89a
-126.0
C
89,89a
-114.7
C
87
(87) K. Bock, C. Pedersen, and L. Wiebe, Acta Chem. Scand., 27 (1973) 3586-3590. (88) K. Bock and C. Pedersen, Acta Chem. Scand., 26 (1972) 2360-2366. (89) G. H. Posner and S . R. Haines, Tetrahedron Left., (1985) 5-8. (89a) R. Csuk and A. Vasella, unpublished results.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
99
TABLEXI 'H- and "F-N.m.r. Data for 2-Deoxy-2-fluoro- and 3-Deo~y-3-fluoro-hexofuranoses Compound H-1 H-2 Jls J2.3
H-3
H-4
H-5
H-6
H-6'
J3.4
54.5
35,6
55.6'
J6.6'
JFJ
JFS
JF,~
JF.5
JF,6
JF.6,
JF,Z
6F
S
References
l-O-Acetyl-3-O-benzyI-2-deoxy-2-8uoro-5,6-O-isopropy~dene-~~-~uco~anose 6.33 5.10 4.28 4.35-4.43 3.97 4.09 -202.8 C 49,50 3.8 2.6 4.5 5.1 5.8 8.6 6.6 51.0 13.0 3-Deoxy-3-fluoro-1,2:5,6~di-0-i90propropy~dene-~~-g~a~ofuranose 4.06- 3.80 -187.9 C 67 5.90 4.72 4.82 4.08 4.34 6.4 8.0 3.9 0.5 3.3 6.9 6.2 15.0 51.6 23.7 3-Deoxy-3-fluoro-D-g~ucofurPnose 1,2-O-isopropylidene-a-, 5,dcarbonate .. 4.50 4.50 -207.1 C 20 4.96 6.00 4.72 5.08 4.41 7.5 6.6 3.9 0.7 2.5 5.1 10.8 49.9 29.2 1,2:5,6-di-O-isopropylidene-a4.03 4.12 -208.0 C 20,44, 4.29 5.95 4.70 5.01 4.11 6.1 8.8 5033, 4.8 3.7 0.8 2.2 8.3 66,82,90 10.5 49.0 28.0 1,2-O-isopropylidene-a- 3.60 -209.4 C 20 4.00 5.08 4.11 5.92 4.66 8.0 2.0 3.3 0.5 50.0 28.8 10.5 5,6-phenylboronate-a4.40 -207.8 C 20 4.00 5.84 4.67 5.07 4.21 0.5 2.0 7.2 3.6 10.5 50.0 28.9 3-Deoxy-3-fluoro-~-idofuranose a anomer -199.9 D 72 ~~
(I
20.0
p anomer
28.0b a
52.0
20.0 -197.0
50.0
D
14.0b
J (H-I, H-3) = 0.7 Hz. Assignments may have to be reversed.
(90) T. J. Tewson and M. J. Welch, J. Org. Chem., 43 (1978) 1090-1092.
72
RENB CSUK AND BRIGITTE
100
I. GLANZER
TABLEXI1 'H- and I9F-N.m.r. Data for 5-Deoxy-5-fluoro- and 6-Deoxy-6-fluoro-hexofuranosesand -hexofurnnosides Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.2
Jz.3
53.4
54.1
55.6
J5.6
56.6'
JFJ
JF,Z
JFJ
JF,~
JF,S
JF,~
JF,~,
SF
~-~eoxy-5-fluoro-1,2-O-~sopropylidene-~~-glucof~anose 5.84 4.47 4.17 4.17 4.74 3.86 3.65 3.5 2.8 7.9 2.4 5.6 13.1 1.6 47.0 30.0 30.0 5-Deoxy-5-fluoro-1,2-O-isopropylidene-~-~-idof~anose 5.92 4.48 4.20 4.27 4.70 3.82 3.77 3.5 7.9 3.6 4.6 12.6 3.8 3.5 14.0 50.0 23.2 19.0 6-Deoxy-6-fluoro-~-glucofuranose 1,2-O-isopropylidene-a5.95 4.54 4.37 4.10 4.18 4.57 4.67 -233.6 2.5 8.0 5.0 3.0 10.0 4.0 25.0 48.0 48.0 1,2-O-isopropylidene-5-O-benzyl-a-234.0 I ,2:3,5-di-O-methylidene-a-226.6
22.2
47.5
48.0
References
C-D
91
C-D
91
A-C
65
92 C
81.93
-213.7
C
81
-229.2
c
81
32.8 48.1 48.1 3,5-O-benzylidene1,2-O-isopropylidene-a36.5 I ,2:3,5-di-O-isopropylidene-ar-
S
47.5
48.0
(91) R.Albert, K.Dax,S . Seidl,H.Sterk,and A. E. Stiitz,J . Carbohydr. Chem., 4(1985) 5 13-520. (92) L. D. Hall and P. R. Steiner,Can. J . Chem., 48 (1970)451-458. (93) H.C. Srivastava and V. K. Srivastava,Carbohydr. Res, 60 (1978)210-218.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
TABLEXI11 'H- and 1 9 F - N . m . r . Data for Pentopyranosyl Fluorides Compound
H-1
H-2
H-3
H-4
H-5
H-5'
J1.2
J2.3
J3,4
J43
54,s'
Js,sf
JFJ
JFJ
JFJ
JFC
JF,~
JF,s,
D-Arabinopyranosylfluoride 3,4-0-acetoxonium-2-O-methyl(Y anomer 4.5-4.6 5.86 5.9-6.0 3.2 55.0 p anomer 5.94 5.9-6.0 4.5-4.6 3.5 52.0 2,3,4-tri-Oacetyl(Y anomer 3.75 4.11 5.35 5.28.0 11.4 2.5 5.3 49.2 5.3 p anomer 3.69 3.49 5.70 5.30 5.30 5.40 1.9 13.1 2.7 10.4 2.0 54.0 25.0 3,4-di-O-acetyl-2-O-methyl-/35.79 3.69 5.26 5.38 4.10 3.83 2.6 10.4 3.5 1.2 1.8 12.8 0.0 51.5 24.3 3,4-0-benzoxonium-2-O-methyla anomer 5.90 6.1-6.25 4.65-4.8 3.0 52.0 p anomer 6.02 6.1-6.25 4.65-4.8 3.5 52.5 2,3,4-tri-O-benzoyl-a5.53 5.79 5.90 5.71 3.86 4.30 3.0 4.5 3.0 4.5 8.3 11.6 49.5 4.3 3,4-di-O-benzoyl-2-0-methyla anomer 4.01 4.37 5.69 5.57 5.55 3.77 7.9 11.3 2.8 5.1 3.5 4.3 49.5 5.7 0.0 ~
6F
S
References
F
94
F
94
-138.4
C
95
-152.8
B
14,95 (I
C
94 b
-137.7
F
94
F
94
B
32,95
C-A
94
(continued)
101
RENE CSUK AND BRIGITTE I. GLANZER
I02
TABLEXI11 (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-5'
J1.2
J2.3
J3,4
J4.5
J4.r
Js,s
JF,~
JF,I
JF,~
J17.4
JFJ
JFJ'
p anomer 6.02 4.10 5.62 5.76 4.34 3.5 2.6 10.2 1.5 2.0 53.0 24.0 0.0 3(or 4)-O-benzoyl-2-O-methyl-p5.66 3.50 4.00 4.30 4.80 3.5 10.0 3.5 2.0 2.0 53.0 25.0 D-Lyxopyranosyl fluoride 2,3,4-tri-O-acetyl-a5.46 5.34.02 5.0 9.5 2.0 49.1 2.0 2,3,4-tri-O-benzoyl-a5.78 5.84.35 1.8 5.3 9.5 48.6 2.0 D-Ribopyranosyl fluoride 2,3,4-tri-O-acetyla! anomer ~
52.1
6F
S
References
4.09 13.2
C-A
94
4.80
C-B
94
3.73 11.0
4.04 10.0
-141.1
95
- 140.7
32,95 n
- 147.7
C
32,95
- 140.4
A
14,15, 32,95
26.3
p anomer
5.60 5.15 5.30 2.6 3.8 2.0 49.5 d5.0 2,3,4-tri-O-benzoyla anomer 5.88 5.35 6.21 3.5 3.1 2.9 53.5 25.3 p anomer 6.05 5.8 5.86 2.0 1.6 4.2 48.0 3.0 D-XylOpymnOSyl fluoride 2,3,4-tri-O-acetyla! anomer 5.67 4.89 5.49 2.8 10.0 10.0 53.5 23.7
5.20 2.0
4.21 3.0
3.92 13.0
(I
5.48 5.5
5.80 2.3
4.05 10.6
4.42 10.9
- 148.1
C
32,95 96
4.56 2.3
4.31 13.4
-139.9
A
32,95 96 a
5.04 6.0
3.97 10.6
3.75 10.6
- 152.1
C
14,15, 95 (1
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
103
TABLEXI11 (continued) Compound H-1 H-2
SF
S
References
4.24 12.5
-136.6
A
95,97
4.58 10.8
4.08 10.8
-151.6
C
32,95
4.20 3.5
4.60 13.1
-137.3
C
32,95
H-3
H-4
H-5
H-5’
J1.2
52.3
53.4
54,s
54.5‘
Js,s
JFJ
JF,Z
JFJ
JF.~
JFS
JFS’
4.90 3.1
3.73 4.3
5.50 6.0 5.30 2.5
p anomer 5.46 4.90 5.06 5.7 3.5 5.7 52.1 7.9 2,3,4-tri-O-benzoyla anomer 5.95 5.37 6.18 10.1 2.8 10.2 53.1 23.5 p anomer 5.75 5.30 5.66 2.5 3.5 3.5 49.0 6.0
3,4-di-0-benzoyl-2-0-methyla anomer
5.83 2.8 52.2
3.62 9.8 24.5 p anomer 5.59 3.57 3.0 5.1 9.0 51.3
0
5.95 9.8
5.36 6.0 1.o
4.19 11.0
3.96 11.3
C
94
5.60 5.3
5.28 3.1
4.47 4.2
3.92 12.8
C
94
Values given for other solvents, too. J (H-I, H-5) = 0.5 Hz. J (H-3, H-5a) = 1.3 Hz; J (H-3, H-5e) = 0.9 Hz.* Refs. 14 and 15 reportedJ (H-2, F-I) = 7. I Hz in C, whereas Refs. 32 and 95 reported 3 Hz. J (H-3, H-5’) = 0.7 Hz. L.
(94) S. Jacobsen, S. R. Jensen, and C. Pedersen, Acta Chem. Scand., 26 (1972) 15611568. (95) L. D. Hall and J. F. Manville, Can. J . Chem., 47 (1969) 19-30. (96) B. Coxon, Tetrahedron, 22 (1966) 2281-2302. (97) L. D. Hall and J. F. Manville, Carbohydr. Res., 4 (1967) 512-513.
RENfi CSUK AND BRIGITTE I. GLANZER
104
TABLEXIV *Hand '9F-N.m.r. Data for 2-Deoxy-2-fluoropento-pyranoses and pyranosides ~~~
Compound H-1 H-2
H-3
H-4
H-5
H-5'
J1.2
JZJ
J3,4
545
54,s'
Js,r
JPJ
Jr.2
JFJ
Jr.4
Jr.5
JPJ'
6F
1,3,4-Tri-0-acetyl-2-deoxy-2-fluoro-~~-arab~nopyranose
6.44 4.0
4.92 5.38-5.46 3.82 4.05 -207.7 10.0 14.0 48.0 10.8 3.5 1.5 Trifluoromethyl3,4-di-O-acetyl-P-~-arnbinopyranoside 5.80 4.90 5.23-5.53 4.13 3.82 -208.0 3.5 9.0 1.5 1.5 13.5 "6.0 46.0 8.0 1.5
1,3,4-Tri-0-acetyl-2-deoxy-2-fluoro-~~-1y~opyranose 5.90 2.4 12.0
4.83 2.4 48.0
5.18
7.2 17.6
4.98-5.09 4.0
4.10 6.0
3.49 12.8
-201.0
S
References
C
48,49, 50
C
53,98
C
4930
C
539
Trifluoromethyl3,4-di-O-acetyl-~-~-lyxopyranoside 3.8 3.8 3.8 3.0 44.2 8.5 2-Deoxy-2-fluoro-~-ribopyranose
2.8
13.1
-214.0
b
%P-
2.3
4.1
7.4
1,3,4-tri-O-acetyla anomer 6.06 4.12 5.48 2.1 2.1 3.5 11.7 8.4 46.9 p anomer 6.23 4.56 5.40 3.2 3.2 6.5 48.0 25.2 5.21 3.0 50.0
6.0 3.0 28.0
100
5.10 3.5
3.13 6.9
4.06 12.1
-202.9
C
49,50, 101
5.19 3.2
4.03 4.8
3.93 12.9
-202.4
C
101
4.26 3.0
4.58 13.0
A
102
C
49SO
1,3,4-Tri-O-benzoyl-P-~-ribose 6.66 3.0 6.5
D
5.75 2.0
2-Deoxy-2-fluoro-~-xylopyranose
I ,3,4-tri-O-acetyl-a4.58 4.94d 6.30 4.3 9.8 5.5 48.0 10.3
5.49d 6.3
4.01
11.5
3.80
11.1
-195.9
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
I05
TABLEXIV (continued) Compound H-1 H-2
H-3
H-4
H-5
H-5‘
JI,Z
12.3
53.4
54,s
J4,5*
J5.5’
JFJ
JF,Z
Jp.3
JF,~
JF,~
JFJ’
SF
S
References
-214.0
C
53,99
Trifluoromethyl 3,4-di-0-acetyl-cu-~-xylopyranoside 3.8 0.5
9.8 48.0
9.5 1.0
9.5
6.5
10.0
Ref. 98 reported a coupling of 0.0 Hz. Ref. 53 reported J (F, H-1) = 6 and J (F, H-3) = 0.0 Hz. Values also given for other solvents. ,IThe assignments may have to be reversed.
(98) (99) (100) (101)
E. L. Albano, R. L. Tolman, and R. K. Robins, Carbohydr. Res., 19 (1971) 63-70. C. G. Butchard and P. W. Kent, Tetrahedron, 27 (1971) 3457-3463. W. K. Olson, J. Am. Chem. Soc., 104 (1982) 278-286. J. T. Welch and S. Eswarakrishnan, J . Chem. Soc., Chem. Commun., (1985)
186- 188. (102) R. J . Cushley, J . F. Codington, and J. J. Fox, Carbohydr. Res., 5 (1967) 31-35.
TABLEXV IH- and 19F-N.m.r.Data for 3-Deoxy-3-fluoro- and 4-Deoxy-4-fluoro-pentopyranosesand -pentopyranosides Compound H-1 H-2
H-3
H-4
H-5
H-5’
51.2
JZJ
J3.4
54,s
J4.5
J5.s
JFJ
JFJ
JF,~
JF,~
JF,S
JFJ’
6F
S
-202.0
H
53
-200.0
H
53
References
3-Deoxy-3-Buoroxylopyraoose b
13.6 57.0 1,2,4-tri-O-acetyl-~a anomer 6.26 4.0 4.0 p anomer 5.71 5.14 4.57 6.5 7.9 7.9 12.4 49.4
12.6
5.07 8.0 12.4
3.48 5.0
4.18 12.2 4.2
-195.3
C
11
C
11,20
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
106
TABLEXV (continued) Compound H-1 H-2
H-3
H-4
H-5
H-5’
JI,Z
J2,3
53.4
J4,5
J4.s
J5.5’
JFJ
JF,~
JF,~
JF,~
JFJ
JF,Y
Benzyl 3-deoxy-3-fluoro-P-~-xylopyranoside 4.39 3.49 4.23 3.78 3.91 3.25 7.6 8.4 8.4 5.6 10.1 11.3 13.4 52.4 13.5 5.7 1.0 Methyl 4-deoxy-4-fluoro-~-arabinopyranoside a! anomer 4.68 4.74 3.5 50.0 p anomer 4.18 3.66 3.68 4.74 3.61 4.10 7.0 2.0 1.0 3.0 13.0 1.5 31.0 49.0 33.0 26.0
S
SF
References
A
103
-201.5
C
65
-205.9
C
65
For the furanoid counterpart, a chemical shift of - 197.5 was reported. For the furanoid counterpart, a chemical shift of - 194.0 p.p.m. was reported; J (F, H-2) = 13 Hz, J (F, H-3)= 55 Hz, and J (F, H-4)= 13 Hz.
(103) A. De Bruyn, M. J. Anteunis, G. Aerts, and E. Saman, Curbohydr. Res., 41 (1975) 290-294.
TABLEXVI ‘H- and I9F-N.m.r. Data for Pentofuranosyl Fluorides
D-Arabinofuranosyl fluoride 2,3,5-tri-O-benzoyl-a!6.17 5.74 5.75 4.95 4.88 0.9 0.5 4.4 3.3 5.8 58.4 6.4 0.7 1.5 3 ,5-di-O-benzoyl-2-O-methylQ anorner 5.91 4.22 5.45 4.81 4.59 0.5 0.8 3.2 5.4 3.8 59.2 6.8 0.5 1.5 p anomer 5.56 3.86 5.69 4.27 4.54 3.5 6.6 5.4 5.6 3.8 63.8 20.3 6.0
A
104
4.65 11.5
A
94
4.75 11.5
C-B
94
4.73 12.1
-123.8
(continued)
107
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
TABLEXVI (continued) Compound H-1 H-2
H-3
H-4
H-5
J1.2
Jz.3
J3.4
54,s
54,s
H-5' Jw
JF,I
JF.2
JFJ
JF,~
JF.5
JF,s*
S
References
C
105.106
c
105
F
107
-122.0
c
107
-128.7
C
107
F
107
SF
2,3,5-tri-O-benzyla anomer 5.78 63.0
9.0
p anomer
5.65
-121.0
66.0 3.0 D-Lyxofuranosyl fluoride 2,3-acetoxonium-5-O-acetyl-a6.27 6.1-6.6 5.0 4.5-4.8 0.0
b
55.0
2,3,5-tri-O-acetyla anomer 63.0
67.0
10.0
p anomer 22.5
0.0
6.5
2,3-benzoxonium-5-O-benzoyl-a6.58 6.3-6.8 0.0 55.0 2,3,5-tri-O-benzoyla anomer 6.03 5.83 6.09 0.8 5.4 6.0 8.5 61.0 p anomer 5.48 6.21 6.10 3.5 5.8 5.8 67.0 21.5 D-Ribofuranosyl fluoride 2,3,5-tri-O-acetyla anomer 67.7
5.6
5.1-5.3
d
c
107
-133.8
C
107
-133.1
c
107
5.06 6.0 2.2
4.6-4.8 6.0
-121.0
5.00 6.0 6.0
4.6-4.8 6.0
r
20.7
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
108
TABLEXVI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-5’
Ji.2
52.3
J3,4
J4,s
J4.5’
Jss,
JFJ
JFJ
JFJ
JF,~
JF,S
JFJ
6F
S
References
p anomer 61.8
4.2
2.3
-116.6
C
107
4.51 11.9
-115.8
A
104
4.42 12.4
-115.5
A
104
6.9
2-0-acetyl-3,5-di-O-benzoyl-p-
5.80 0.5 60.9
5.55
4.7 4.7
5.74 6.9 2.4
4.79 3.5 6.7
4.68 4.6
3-O-acetyl-2,5-di-O-benzoyl-p5.95 0.5 61.6
5.70 5.0 4.5
5.62 5.0 1.7
4.74 4.5 7.9
4.68 5.4
6.04 5.81 5.75 0.5 4.9 4.9 61.3 4.9 2.1 2,3,5-tri-O-benzoyla anomer 6.30 5.51 5.86 3.2 6.9 2.3 64.4 20.6 0.0 p anomer 6.18 5.96 6.02 0.5 4.8 5.8 61.5 4.8 2.2 2,3,5-tri-O-benzyla anomer 5.64 3. I 66.0 24.0 p anomer 5.63
4.82 3.6 7.2
4.61 5.3
4.25 12.1
-115.7
4.93 3.1 1.0
4.76 3.5
4.61 12.1
-133.3
5.11
4.89 5.2
4.69 12.2
-115.9
0
5-O-acetyl-2,3-di-O-benzoyl-p-
63.5 D-Xylofuranosyl fluoride 2,3,5-tri-O-acetyla anorner 5.95 5.13 5.56 3.6 6.5 6.5 61.8 17.2 p anorner 5.63 5.18 5.34 1.0 0.5 5.5 60.5 5.2 0.5
3.9 6.6
A
104 a
A
104 (1
A
104 a
-133.0
C
106
-116.0
C
106
4.74 4.8 1.4
4.31 4.1
4.13 12.4
-134.8
C
107
4.70 5.3 5.2
4.29 7.1
4.20 11.4
-113.2
C
104
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
109
TABLEXVI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-5’
JIJ
J2.3
J3,4
54.5
JW
JS,Y
JF.1
JF,2
J F ~
JF,~
JFJ
JF,s~
2,3,5-tri-O-benzoyl-p-
S
SF
References
C
107
F
94
4.48
C
94
5.69 4.96 4.70 4.70 5.2 5.5 6.5 62.6 5.9 6.0 3,5-benzoxoniurn-2-O-rnethyl-~6.09 4.85 5.97 5.97 5.4 0.0 0.5 4.2 60.0 4.0
C
94
F
94
5.96
5.67
5.09 4.5-4.8 6.0 6.0 61.5 4.5 6.0 3,5-acetoxoniurn-2-O-rnethyl-/36.03 4.6 5.72 5.72 5.2 0.0 4.0 61.0 3.5 3,5-di-O-benzoyl-2-O-rnethyla anorner
5.91 3.6
62.5
4.22
6.2 18.0
5.95 5.8
5.78 6.7
p anomer
5.84
4.98 5.9 1 .o
4.48 5.9
-118.5
4.13 1.0
a Also reported for a solution in C. Ref. 106 reported the data for the L enantiorner. J (F-1, Me-C+) = 2.90 Hz. d J (F-1, Me-C’) = 2.90 Hz. e.J (H-I, H-3)= 0.6 Hz.
(104) L. D. Hall, P. R. Steiner, and C. Pedersen, Can. J . Chem., 48 (1970)1155-1165. (105) W. Rosenbrook, Jr., D. A. Riley, and P. A. Lartey, Tetrahedron Lett., (1985)3-4. (106)T.Mukaiyama, Y. Hashimoto, and S. I. Shoda, Chem. Lett., (1983)935-938. (107) K.Bock and C. Pedersen, Acta Chem. Scand., Ser. B , 30 (1976)727-732. TABLEXVII
IH-and 19F-N.m.r. Data for 2-Deoxy-2-fluoropento-furanoses and -furanosides Compound H-1 H-2
H-3
H-4
H-5
H-5’
JI,~
52.3
J3.4
54,s
J4,v
Js.5
JFJ
JF.~
JFJ
JF,~
JFJ
JFJ,
2-Deoxy-2-fluoro-~-arabinofuranose Sphosphate, sodium salt a anorner 5.30 4.90 0.0 0.0 9.5 68.0
SF
S
D
References
66 (1
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
I10
TABLEXVII (continued) Compound H-1 H-2
H.3
H-4
H-5
H-5'
51.2
52.3
53.4
54.5
54,s
JW
JFJ
JF,~
JF,~
JF,~
JF,S
JF,~
p anomer
5.20 4.0 12.0
66 (1
68.0
1,3-di-O-acetyl-5-0-benzoyl-a5.0 5.24 4.51 48.0 5.10 49.0
C
108
A
109
C
108
N
110
C
109
C
108
C
I08
22.0
1,3-di-O-acetyl-5-0-benzyl6.26 0.7 10.5
References
S
D
4.80
6.33
10.0
6F
5.25 4.5 22.8
4.47 4.5
3.74
3.74
1-0-acetyl-5-O-benzoyI-3-O-formyl-a-
6.45 5.12 5.45 4-. 0.0 9.5 50.0 22.0 1,3,5-tri-O-benzoyl-a6.7 5.4 5.61 4.749.0
1,3-di-O-benzoyl-5-0-benzyl6.75
5.50
9.0 49.0 5-O-benzo yl-
5.60 3.4 19.5
4.67 5.0
3.86
3.86
a anomer
5.3 0.0 9.5
4.98 0.0 68.0 p anomer 5.28 4.89 3.5 12.0 68.0 1,3,5-tri-O-benzyl-a5.25 5.03 4.36 1.0 2.4 7.3 12.8 51.2 5-0-benzyl5.42 4.87 4.23 3.86 1.6 6.0 9.7 50.0
3.86
3.63
C
111
3.56
3.56
C
109
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
III
TABLEXVII (continued) Compound
H-1
H-2
H-3
H-4
H-5 H-5’
Ji.2
J2.3
J3,4
54.5
54,s.
Js,sf
JFJ
JF,Z
JF3
JF,~
JFS
JF,S
SF
Methyl 2-deoxy-2-fluoro-a-~-arabinofuranoside 4.96 4.85 3.70 4.5 1.0 2.6 12.0 52.0 3.5-di-0-benzyl5.09 1.o 12.0
S
References
A
109
C
112
5-0-benzyl5.06 4.82 4.10 3.64 3.64 C 109 I .6 5.5 10.3 51.0 1-0-Acetyl-2-deoxy-2-fluoro-5-0-(methoxymethyl)-a-D-nbofuranose 6.40 5.07 4.29 4.52 3.69 3.72 -216.8 C 49,50 10.1 4.4 5.6 2.4 51.3 4.4 Methyl 3-O-benzoyl-5-O-benzyl-2-deoxy.2-fluoro-&noside 5.08 5.00 5.64 4.71 3.71 3.71 C 1 I3 1.6 5.5 5.5 13.4 49.5 16.5 J (C-S, P) = 8 Hz.
(108) U. Reichrnan, K. A. Watanabe, and J. J. Fox, Carbohydr. Res., 42 (1975) 233-240. (109) J. A. Wright, N. F. Taylor, and J. J. Fox, J . Org. Chem., 34 (1969) 2632-2636. (I 10) C. H. Tann, P. R. Brodfuehrer, S. P. Brundidge, C. Sapino, Jr., and H. G. Howell, J . Org. Chern., 50 (1985) 3644-3647. (111) T. L. Su, R. S. Klein, and J. J. Fox, J. Org. Chem., 47 (1982) 1506-1509. (112) T. L. Su, R. S. Klein, and J. J. Fox, J . Org. Chem., 46 (1981) 1790-1792. (113) J. A. Wright and J. J. Fox, Carbohydr. Res., 13 (1970) 297-300.
RENfi CSUK AND BRIGITTE I. GLANZER
I12
TABLE XVIII 'H- and 19F-N.m.r. Data for 3-Deoxy-3-fluoro-D-pento-furanosesand -furanosides Compound H-1 H-2
H-3
H-4
H-5
H-5'
JIJ
J2.3
53.4
J4.5
54,s
J5.5'
JFJ
JF,~
JFJ
JF.~
JFJ
JF.~'
SF
S
Methyl 2,5-di-O-benzoyl-3-deoxy-3-fluoro-~~-arabinofuranoside -188.0 C
References
53,71
7.0" 46.0 10.0" 3-Deoxy.3-fluoro-1,2-O-isopropyl~dene-5-O-~tolyls~onyl-~-~-~lofuranose 5.86 4.64 4.90 4.70 4.10 -210.6 C 20 3.8 0.5 2.0 7.0 10.5 50.5 25.0 Methyl 2,5-di-O-benzoyl-3-deoxy.3-fluoro-/3-~-xylofuranoside -203.0 C 53,7 1 15.0 56.0 24.0 3-Deoxy-3-fluoro-1,2-O-isopropylidene-~-~-~y~~-pentodi~do-l,4-furanose 6.16 4.76 5.25 4.62 9.67 -205.5 C 114 3.7 0.5 2.6 1.2 10.0 50.0 31.5 The assignments may have to be reversed.
(114) J. M. J. Tronchet, B. Gentile, A. P. Bonenfant, and 0. R. Martin, Helv. Chim. Acfa, 62 (1979) 696-699.
TABLE XIX 'H- and lgF-N.m.r. Data for 5-Deoxy-5-fluoro-~-pento-furanoses and -furanosides Compound H-1 H-2
H-3
H-4
H-5
H-5'
JI,~
52.3
J3.4
54.5
54,s
J5.5,
JF,I
JFJ
J F ~
JF.~
JFJ
JFJ-
6F
S
References
-227.3
D
81
-232.5
C
81
-232.1
C
81
5-Deoxy-5-fluoro-~-ribofuranose 23.5 50.0 Methyl 5-deoxy-5-fluoro-~-ribofuranoside 2,3-di-O-acetyl29.5
47.5
50.0
47.5
2,3-O-isopropylidene(Y anorner 30.0
47.5
47.5 (continued)
I 13
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLEXIX (continued) Compound H-2 H-1
SF
S
References
-224.8
C
81
10.5 47.5 47.5 3-0-Benzyl-5-deoxy.5-fluoro-1,2-O-isopropyl~dene-~-~-xy~ofuranose 5.94 4.60 3.97 1.45 4.64 4.58 C 3.4 0.7 3.0 9.0 16.0 42.0 42.0
115
H-3
H-4
H-5
H-5'
Ji,z
52.3
53.4
54.5
J4.5
Js,5*
JF.I
JFJ
JFJ
JF.~
JF.~
JF.~'
p anorner
(115) P. W. Kent and R. C. Young, Tetrahedron, 27 (1971) 4057-4064.
TABLEXX 'H- and I9F-N.m.r. Data for Fluorinated 1,5-Anhydrohexopyranose Derivatives Compound H-2 H-1
H-3
H-4
H-5
H-6
H-6'
JI,Z
JZ,3
53.4
54,5
55.6
Js,~
56.6'
JFJ
JF,Z
JF,~
JF,~
JF,~
JF.6
JF,~
SF
S
References
3,4,6-Tri-0-acetyl-1,5-anhydro-2-deox~2-fluoro-l-C-methyl-~-~-glucopyranose 4.32 4.53 5.23 4.76 3.80 4.19 3.92 C 39 0 5.9 8.8 8.8 9.4 5.0 2.5 12.1 1.5 49.5 12.6 1,5-Anhydro-6-deoxy-6-fluoro-~-ara6~~~-hex-l-enitol 3,4-di-O-acetyl- 1,2-dideoxy6.61 4.90 5.0-5.48 4.15-4.75 5.0-5.48 A 116 b 6.6 3.2 47.0 3,4-di-O-benzyl117 6.39 4.4-5.1 4.1-4.35 3.7-4.1 4.1-4.35 4.4-5.1 -235.4 C 4-0-benzyl-3-deoxy6.29 4.5-4.8 2.27
24.6
47.2
3.47-4.50 29.4
47.2 4.67
48.0
-235.8
C
1 I7
48.0
" M e : 8 = 1 . 3 6 , J ( F , M e ) = 2 . 6 , a n d J ( H - l , M e )=6.9Hz. b J ( H - I , H - 3 ) = 1.2Hz.
(116) M. Sharma and W. Korytnyk, Carbohydr. Res., 83 (1980) 163-169. (117) I. D. Blackburne, P. M. Fredericks, and R. D. Guthrie, Aust. J . Chem., 29 (1976) 381-391.
RENE CSUK AND BRIGITTE I. GLANZER
1 I4
TABLEXXI
'H-and 19F-N.m.r.Data for Fluorinated 1,6-AnhydrohexopyranoseDerivatives Compound
H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JI,Z
Jz.3
J3,4
54.5
55.6
55.6
56.6
JF,~
JF,Z
JF,~
JF,~
JF,S
JF,6
JF.6'
6F
S
References
1,6-Anhydro-2-deoxy-2-fluoro-/3-~-glucopyranose 3,4-di-O-acetyl5.51 4.24 5.00
4.64
4.64
C
118,119
17.0 45.0 3-0-acet yl-4-0-benzyl5.51 4.25 5.14
3.25
4.60
C
118,119
3.35 1.4
4.4-4.7
C
I20
45.0 17.0 3,4-di-O-benzyl5.53 4.35 3.6-3.8 I .4 4.9 45.0
3.6-3.8 1.2
3.91 1.3
2-O-Acetyl-1,6-anhydro-4-O-benzyl-3-deoxy-3-fluoro-/3-~-~tropyranose 5.52 1.5
6.5
5.23 9.0 13.0
4.78 4.5 48.0
3.9-3.99
4.65
C
118,119
2,4-Di-0-acetyl-1,6-anhydro-3-deoxy-3-fluoro-/3-~-idopyranose
-202.1 c 0.0 4.5 8.0 0.0 4.5 4.5 1,6-Anhydro-3-deoxy-3-fluoro-/3-~-mannopyranose 5.43 3.83 4.74 4.12 4.63 4.09 3.81 D 1.9 4.5 2.0 2.0 1.2 6.0 1.9 0 26.4 47.1 12.5 0.8 1.4 3.8 2,4-di-O-acetylC 5.49 4.15-5.01 5.04 4.65 4.20 3.88 1.6 1.8 I .2 5.9 1.9 0.0 12.6 0.0 1.3 3.5 3-~-Acetyl-1,6-anhydro-2,4-dideoxy-/3-~-glucopyranose 4-acetamido-2-fluoro5.52 4.27 4.84 4.10 4.50 4.19 3.80 C 2.5 1.5 1.5 2.5 I .o 6.0 8.0 1.0 43.0 15.0 2-acetamido-4-fluoro5.34 3.99 4.86 4.29 4.56 3.89 3.65 1.5 1.5 1.5 1.5 1.5 5.0 8.0 1.5 15.5 45.0 11.0 1.5 5.0 1,6-Anhydro-2,4-dideoxy.2-fluoro-/3-~-e~~~~o-hexop~anos-3-ulose 4.63 4.20 2.91a 2.40e 4.83 3.75 3.64 N 1.9 5.6 I .3 0.5 4.0 7.8 2.0 49.0 2.0 4.5
8.0 16.0
8.0 50.0
12
4.5 16.5
I
73 h
73
121 c
6,121 P
122
r.Y
For the nonacetylated derivative, a shift of 6F = -198.2 for a solution in D was reported. Also reported, in C. ' J (H-I, H-3)= 1.50, J (H-2, H-4) = 1.0, J (H-3, H-5) = 1.5 Hz. Solvent: 5 : 1 : 1
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
I IS
chloroform-dimethyl sulfoxide-hexafluorobenzene. J (H-I, H-3) = 1.5, J (H-1, H-5) = 1 .O Hz. f J (H-4, H-4') = 17.7 Hz. The symbol a stands for the axial, and e for the equatorial, proton at C-4.
(118) J. Paciik, J. PodeSva, Z. ToCfk, and M. (?ern$, Collect. Czech. Chem. Commun., 37 (1972) 2589-2599. (119) J. Pachk, Z. ToEfk, and M. Cernf, Chem. Commun., (1969) 77. (120) T. Haradahira, M. Maeda, Y. Kai, and M. Kojima, J . Chem. Soc., Chem. Commun., (1985) 364-365. (121) J. Pacak, P. DraSar, D. Stropovit, M. Cern$, and M. BudCSinsk$, Collect. Czech. Chem. Commun., 38 (1973) 3936-3939. (122) J. DoleZalovB, M. Cerny, T. Tmka, and J. Pacak, Collect. Czech. Chem. Commun., 41 (1976) 1944-1953. TABLEXXII 'H- and 19F-N.m.r.Data for Fluorinated 3,6-Anhydrohexose Derivatives Compound H-2 H-1
H-3
H-4
H-5
H-6
H-6'
J1.2
J2,3
53.4
54,s
55,6
55,6'
56.6'
JF.1
JF,Z
JFJ
JF,~
JFJ
JF,~
Jv.6
2-0-Acetyl-3,6~nnhydro-S~O-benzoyl-~-idofuranosyl fluoride a anomer
6F
S
-138.0
A
p anomer 5.72 5.28 5.06 4.72 5.56 4.42 4.06 -119.8 A 0.8 0.5 4.8 1.0 4.0 1.5 10.6 62.3 5.8 0.5 4.8 1.5 3,6-Anhydro-5.deoxy-S-fluoro.1,2-~-isopropylidene-~-~-glucofuranose -207.6 B 1.6" 5.8O 51.6 19.5 3,6-Anhydro-5-deoxy-S-fluoro-~-idofuranose 1 ,2-di-Qacetyla anomer 4.28 4.93 5.14 5.10 4.68 6.12 1.0 0.5 3.0 0.5 4.6 0.5 39.8 10.8 50.6 2.7 0.5 1.0 p anomer 5.08 3.91 4.97 6.34 4.94 4.88 0.5 2.8 0.8 0.5 3.3 4.4 50.6 38.1 8.1 0.5 1.0 2.0 1,2-O-isopropylidene-p4.70 3.59 4.71 4.32 4.59 5.59 0.5 2.8 0.8 0.5 3.2 3.5 38.3 7.5 50.4 0.5 1.5 1.5 a
References
22
22
92,123
17.9
4.00 11.4 25.5
-186.7
A
92
4.08 11.6 22.3
-190.8
A
92
3.75
-189.7
B
92
11.1
26.1
Assignments may have to be reversed.
(123) R. Csuk and B. I. Glanzer, unpublished results.
RENE CSUK AND BRIGITTE I. GLANZER
116
IH-
TABLEXXIII and I9F-N.m.r. Data for Fluorinated Sugar Acids and Lactones
(D-Glucofuranosylfluoride)urono-6,3-lactone 2,S-di-O-acetyl-P5.91 5.35 5.23 5.36 5.63 0.6 0.5 4.6 6.3 60.1 4.5 0.5 4.4 0.5 2,S-di-O-benzoyl-P6.2 5.7 5.56 5.71 5.98 0.5 0.5 4.6 6.3 60.1 4.0 0.5 4.6 0.3 ~-Deoxy-3-fluoro-~-gluconic acid
-118.3
A
22 a
-118.5
A
22 a
-207.0
D
70
Methyl (methyl 4-deoxy-4-fluoro-cu.~-glucopyranosid)uronate -119.2
M
124
14.7
54.5
5-Deoxy-5-fluoro-1,2-O-isopropylidene-cu-~-glucofuranurono-6,3-lactone 6.08 3.6
4.87 4.90 5.08 5.33 -216.3 C 91 0.6 2.8 4.0 b 3.5 I .3 1.0 48.0 5-Deoxy-5-fluoro-&~-idofuranurono-6,3-lactone 1,2-O-benzylidene6.17 5.09 5.40 5.22 5.09 -199.0 c 125 3.6 0.0 4.0 0.0 0.0 10.0 47.5 I ,2-O-isopropylidene5.95 4.87 5.10 4.96 4.93 -199.7 C 91 3.7 3.3 0.4 1.2 8.7 48.3 Methyl [benzyl 2-(benzyloxycarbonyl)amino-2,3,4-tndeoxy-5-fluoro-~-~-e~~~ro-hex-3enopyranosid]uronate 4.88 4.75 5.75 5.46 B 126 3.5 10.0 d 1 .O 1 .O " J (H-3, H-5) = 0.5 Hz. * J (H-2, H-4) = 0.5 HZ. ' J (H-3, H-5)= 0.4, J (H-2, H-4) = 0.3 Hz. Assignments of H-3 and H-4 may have to be reversed; some values were also given for C as the solvent.
(124) J. Samuel and N. F. Taylor, Carbohydr. Res., 133 (1984) 168-172. (125) R. Albert, K. Dax, U. Katzenbeisser, H. Sterk, and A. E. Stiitz, J. Carbohydr. Chem., 4 (1985) 521-528. (126) J. Kiss, P. C. Wyss, G. Flesch, W. Arnold, K. Noack, and P. Schonholzer, J . Carbohydr. Chem., 4 (1985) 347-361.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
I 17
TABLEXXIV IH- and UF-N.m.r. Data for Aminodeoxyhexopyranosyl Fluorides (and Their Synthetic N-Containing Precursors) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JLZ
JZJ
J3,4
J~J
55.6
5 5 , ~
56.6
JFJ
JF,Z
JFJ
JF.4
JFJ
JF,6
JF,~
3-Azido-4,6-0-benzyldene-3-deoxy-~~-allopyranosyl fluoride 5.53 8.0 52.0
3.50 3.5 12.5
4.20 3.0 3.4
3.60 9.0
3.99 9.0
3.72 5.0
4.37 9.0
-147.3
2-Acetamido-2-deoxy-~-~-glucopyranosy~ fluoride 5.18 7.8 54.0
11.0 3,4,6-tri-O-acetyl5.39 6.8 53.0 13.0
S
References
C
I27
M
128
C-M
128
(127) S. Castillon, A. Dessinges, R. Faghih, G. Lukacs, A. Olesker, and T. T. Thang, J. Org. Chem., 50 (1985) 4913-4917. (128) F. W. Ballardie, B. Capon, W. M. Dearie, and R. L. Foster, Carbohydr. Res., 49 (1976) 79-92.
TABLEXXV 'H- and "F-N.m.r. Data for 3-Amino-2,3-dideoxy-2-fluoro-a-~-altropyranoside Derivatives (and Their N-Containing, Synthetic Precursors) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JI,Z
52.3
53.4
J4.5
55.6
5 5 , ~
36.6
JFJ
511.2
JFJ
JF,~
JF,~
JF,~
JF,~
SF
4,6-0-Benzylidene-2,3-dideoxy-2-fluoro-a-~-~tropyranoside methyl 3-amino4.77 4.66 3.57 -189.2 0.2 2.6 2.6 9.8 43.8 11.6 benzyl 3-azido4.90 4.63 4.29 4.09 4.29 3.77 4.29 -190.8 0.0 2.5 4.0 9.5 10.5 10.5 11.5 43.5 11.5 3.0
S
References
C
129
C
127
(continued)
TABLEXXV (continued) Compound
S
References
3.92 10.0
C
128
4.29
C
127
H-1
H-2
H-3
H-4
H-5
J2,3
J3.4
J4,a
$5.6
H-6 Js,~
H-6’
JIS JFJ
JF,Z
JFJ
JF.4
JF,S
JF.~
JF,~
4.17 10.0 2.5
4.11 4.0
4.37 10.0
benzyl 3-benzarnido5.12 4.77 5.14 1.0 4.5 44.0 8.5
6F
56.6‘
Benzyl2,3-dideo~y-2-fluoro-cu-~-altropyranoside 3-azido-6-O-he .~ thvlsulfonvl)4.92 4.67 4.04 4.17 2.0 12.0 43.0 3-benzarnido5.42 5.14 5.51 4.81 4.34 1.0 4.0 9.5 44.0 3-benzamido-6-0-mesyl5.19 4.72 4.97 4.2-4.00 1.0 4.0 1.5 7.5 45.0
4.46
10.0
-
4.60
P
128
4.64
4.49 11.0
C
128
C
128
C
I30
5.5
3-benzarnido-6-O-tos yl-
4.45 4.20 5.06 4.62 4.87 4.03-3.95 1.0 3.0 1.5 11.0 10.0 8.0 45.0 Methyl 3-benzamido-2,3-dideoxy-2-fluoro-cu-~-al~opyranoside 4,6-di-O-acetyl4.92 4.60 5.13 5.18 4.12 4.25 - 193.3 1.5 3.5 4.5 10.0 4.0 4.0 8.0 45.0 8.6 1.5 4,6-di-O-benzoyl5.00 4.67 5.35 5.63 4.40 4.67 4.47 -193.7 1.5 3.6 4.6 9.6 2.6 6.0 12.0 8.0 44.0 9.0 2.0 4,6-O-benzylidene4.85 4.29 5.06 3.87 -191.4 2.5 9.0 1.5 3.0 8.5 1.0 9.0 45.0 Methyl 4,6-0-benzylidene-2,3-dideoxy-2-fluoro-cu-~-al~opyranoside 3-(diallylarnino)4.70 - 182.6 18.5 13.0 42.5 3-(trifluoroacetarnido)4.89 4.66 4.89 1.4 3.0 4.5 7.5 45.0 7.5
4.32 9.8
3.95 4.2
“ J ( H - I , H-3) = 1.2 Hz. b J ( H - l . H-3)
=
4.08 9.8
3.85 9.8
1.5 Hz. ‘J(H-1, H-3)
-191.6
=
1.5 Hz.
‘ I
C
130 b
C
130 c
C
131
C
131
I I9
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
(130) L. Hough, A. A. E. Penglis, and A. C. Richardson, Carbohydr. Res., 83 (1980) 142- 145. (131) D. Picq and D. Anker, J . Carbohydr. Chem., 4 (1985) 113-123. TABLEXXVI 'H- and 19F-N.m.r. Data for Aminodideoxy-3(or 4)-flUOrO Sugars (and Their N-Containing Synthetic Precursors)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JI,~
J2.3
53.4
J4.5
55.6
JS,C
56.6,
JFJ
JFJ
JF,3
JF,4
JF.5
JF.6
JF,C
6F
Methyl 6-azido-3,6-dideoxy-3-fluoro-~-~-allopyranoside 4.52 3.47 4.89 3.61 3.84 3.48 3.48 -217.4 10.0 8.5 2.0 2.0 2.0 29.0 53.0 28.0 4,6-0-Benzylidene-2,3-dideoxy-3-fluoro-a-~-glucopyranoside benzyl 2-acetamido5.05 3.88-3.97 4.78 3.88-3.97 4.28 3.85 4.0 9.0 10.0 4.0 10.0 10.0 60.0 2.0 benzyl 2-azido5.03 3.47 5.03 3.78 3.91 3.78 4.26 -198. 10.0 4.0 9.0 9.0 9.0 9.0 4.5 5.5 9.0 54.5 2.0 methyl 2-benzamido4.89 4.43 4.97 4.05 3.72 4.28 3.87 3.7 9.8 9.4 9.0 4.8 10.3 10.0 3.0 12.1 53.6 12.4 0.7 1.9 Methyl 3,6-di-0-ace:etyl-2,4-dideoxy-4-fluoro-a-~-glucopyranoside 2-acetamido4.67 5.30 4.70 -199.8
S
References
A
65
C
132
C
I27
S
133
P
134
14.7 49.7 2-benzamido4.83 4.42 5.48 4.59 4.42 4.44 -196.9 C I34 3.3 11.3 9.7 9.7 1.8 11.3 3.3 13.0 49.7 4.4 Benzyl 2-acetamido-3-O-ace:etyl-2,4-dideoxy-4-fluoro-6-O-tn:etyl-a-~-g~opyranoside 5.05 -188.2 C 135 4.0 54.0 Methyl 4,6-dideoxy-4-fluoro-a-~-talopyranoside 6-azido4.87 4.70 3.93 3.35 3.68 -216.1 A 65 0.0 5.0 8.0 12.0 51.0 30.0 2.0 (I
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
120
TABLEXXVI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
Jl,Z
J2,3
J3.4
J4,S
55.6
J5.6'
56.6'
JF,~
JFJ
JFJ
JF.4
JF,S
JF,~
JF.6'
3.68
4.67
3.90
3.37
6-amino4.69 3.64 0.0
32.0
51.0
3.37
6F
S
References
-217.0
A
65
31.0
Data also reported for P as the solvent.
(132) L. H. B. Baptistella, A. J. Marsaioli, J. D. De Souza Filho, G. G. De Oliveira, A. B. DeOliveira, A. Dessinges, S. Castillon, A. Olesker, T. T. Thang, and G. Lukacs, Cnrbohydr. Res., 140 (1985) 51-59. (133) H. H. Baer and A. Jaworska-Sobiesiak, Cnrbohydr. Res., 140 (1985) 201-214. (134) L. Hough, A. A. E. Penglis, and A. C. Richardson, Cnn. J . Chem., 59 (1981) 396-405. (135) M. Sharma and W. Korytnyk, Cnrbohydr. Res., 79 (1980) 39-51. TABLEXXVII 'H- and I9F-N.m.r. Data for Aminodideoxy-6-luoro Sugars
2-Acetamido-l,3,4-tri-O-acetyl-2,6-dideoxy-6-fluoro-~-gda~opyranose -230.8 C 18.5 47.5 47.5 Methyl 2,6-dideoxy-6-fluoro-cu-~-gdactopyranoside 2-acetamido15.8
2-acetamido-3,4-di-O-acetyl4.78 5.16 5.38 3.5 11.0 3.2 1.0
47.5
-235.0
P
134
-238.0
C
134
-234.9
C
134
-236.2
C
134
47.5 4.40
46.0
85
46.0
2-benzamido14.5
3,4-di-O-acetyl-2-benzamido-
4.98 3.5
10.0
5.29 3.5
5.50
1.0
46.0
46.0
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
121
TABLEXXVII (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.2
J2,3
53.4
54,s
55.6
55.6
J6.6,
JF,l
JFJ
JFJ
JF,~
JFJ
JF,6
JF,~
2-benzamido-4-0-benzo yl-3-0-benzyl-
5.03 3.3
10.5
3.80 3.2
5.84 1.3
2-benzamido-3-O-benz yl-
14.5 48.5 48.5 2-Acetamido-2,6-dideoxy-6-fluoro-~-glucopyranose a anomer 5.86 5.26 4.18 3.2 2.7 29.3 48.1 48.7 I ,3,4-tri-O-acetyla anomer 6.17 4.44 3.97 4.42 3.5 25.0 48.5 48.5 p anomer
SF
S
-236.2
C
134
-235.2
C
134
-238.0
P
134,136
-238.0
C
85,134
-232.5
C
85
P
85,136
21.8 48.2 48.2 2-Acetamido-2,6-dideoxy-6-fluoro-cu-o-glucopyranoside benzyl 3,4-di-O-benzyl-232.8 5.21 5.02 4.55 3.6 2.5 29.0 47.5 47.5 methyl 3,4-di-O-acetyl-236.1 3.64 4.46 4.14 4.32 5.06 5.16 3.5 10.0 10.0 10.5 23.5 48.5 48.5 methyl 3,4-di-O-methyl-233.4 4.92 4.41 4.95 3.4 2.4 27.5 48.0 48.0 Methyl 2-benzamido-2,6-dideoxy-6-fluoro-a-~-glucopyranoside -239.0 26.0 3,4-di-O-acetyl4.87 4.51 5.40 3.5 10.0 10.0
5.12 10.0
49.5
3.98 23.5
a
P
134
P
136
A
134
A
134
49.5 4.46
48.5
References
-237.4
48.5 (continued)
RENB CSUK AND BRIGITTE I. GLANZER
I22
TABLEXXVII (continued) Compound H-1 H-2
6F
S
References
-239.1
C
134
-231.8
C
134
A
65
A
65
D
1 I6
-237.3
D
I I6
4.95
-234.1
s
1I6
1,3,4-tri-O-acetyla anomer 5.19 1.6
-234.3
C
85,116
-233.1
C
85,116
H-3
H-4
H-5
H-6
H-6'
J1.2
JZJ
J3,4
54,s
Js,6
55.6'
J6,v
JF.1
JF,~
JFJ
Jp.4
Jp.5
JF,~
JF,6'
3-0-benzyl28.0
49.5
49.5
3-0-benzyl-4-O-mes yl-
22.5 41.4 41.5 Methyl 4,6-dideoxy-6-fluoro-cu-~-glucopyranoside 4-azido4.14 3.50 3.60 4.60 4.60 -234.1 10.0 3.5 26.0 46.0 46.0 4-amino4.1 3.92 4.25 4.33 -233.8 4.0 10.0 4.0 1.5 10.0 28.5 48.0 48.5 2-Amino-2,6-dideoxy-6-fluoro-~-mannopyrmose hydrochloride (I anomer -231.5
p anomer
21.9
21.5
45.9
41.0
45.9
41.0
2-Acetamido-2,6-dideoxy-6-fluoro-~-mannopyranose
p anomer
25.5
41.2
41.2
6.01 1.8
23.8
41.5
41.5
Ref. 85 reported J (H-5, F) = 22.5 Hz.
(136) M. L. Shulman and A. Ya. Khoriin, Carbohydr. Res., 21 (1913) 141-141.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
123
TABLEXXVIII 'H- and I9F-N.m.r. Data for 3-Amino-2,3,6-trideoxy-2-fluoro-6-halogeno-cr-~altropyranoside Derivatives (and Their N-Containing Synthetic Precursors)
Benzyl 2,3,6-trideoxy-2-fluoro-6-iodo-a-~-altropyranoside 3-azido4.88 4.61 3.71 4.06 3.45 3.21 C 121 3.0 10.5 10.5 2.5 11.0 12.0 44.0 3-benzamido5.20 4.10 4.92 3.99 3.87 3.16 3.32 C 132 1.0 3.5 2.5 10.0 2.0 9.0 11.0 1.5 43.0 2.0 Methyl 4-0-benzoyl-6-bromo-2,3,6-trideoxy-2-fluoro-cr-~-altropyranoside 3-benzamido5.03 4.70 5.30 5.40 4.25 3.61 3.51 C 132,133, 1.5 3.5 4.0 10.0 2.4 8.2 10.9 137 8.0 44.5 9.0 2.0 3-(trifluoroacetamido)4.99 4.63 5.03 5.38 4.16 3.60 3.5 -204.0 C 131 10.8 8.0 1.3 3.0 4.3 10.8 2.5 1.7 44.3 1.7 (137) M. K. G u j a r , V. J. Patil, J. S. Yadav, and A. V. Rama Rao, Carbohydr. Res., 135 (1984) 174-177. TABLEXXIX 'H- and I9F-N.m.r. Data for 3-Amino-2,3,6-trideoxy-2-fluoro-hexopyranoside Derivatives (and Their N-Containing Synthetic Precursors) Compound H-1 H-2 Jls J2.3 JF.1
JF,2
H-3
H-4
H-5
H-6
H-6'
J3c
J4,5
554
J5,6'
J6.6
JFJ
JF.4
JFJ
JF.6
J F . ~
SF
Benzyl 3-benzamido-2,3,6-trideoxy-2-fluoro-cr-~-altropyranoside 4.65 4.12 4.97 3.91 3.83 1.43 2.0 2.0 7.0 8.0 45.0 Methyl 2,3,6-trideoxy-2-fluoro-a-~-altropyranoside 3-amino4.75 4.57 3.45 3.26 3.60 1.34 1.6 3.2 10.0 6.2 10.2 45.5
S
References
C
132
C
133 a
(continued)
RENB CSUK AND BRIGITTE I. GLANZER
124
TABLEXXIX (continued)
Compound
H-1
H-2
H-3
H-4
H-5
H-6
H-6'
JIJ
J2.3
J3,4
J4.5
55.6
J5.6,
564'
JF.1
JF.2
JFJ
JF,~
JFJ
Jw.6
JF,~
5.28 9.8 2.0
4.16 6.3
3.83 9.0
3.76 6.6
3-benzamido-4-O-benzo y l-
4.92
4.67 5.23 3.2 4.0 8.0 45.3 8.5 3-(trifluoroacetamido)4.84 4.60 4.13 1.5 3.5 4.5 7.8 45.0 9.0 1.5
SF
S
C
1.32
References
133 137 0
I .36
C
133 0
2,3,6-Trideoxy-2-fluoro-~-galactopyranose 3-amino-, hydrochloride (I! anomer 5.29 4.15 3.74 3.83 4.21 1.18 -192.2 3.5 10.5 3.5 1.0 6.5 0.0 50.4 11.0 p anomer 4.15 4.40 3.55 3.83 3.76 1.25 -192.4 7.7 10.0 3.5 6.5 3.0 52.0 11.2 I -O-acetyl-4-O-benzoyl-2-fluoro-3-(tnfluoroacetamido)-~5.90 4.70 4.60 5.63 4.13 1.26 8.0 10.0 2.0 1.0 7.0 4.0 45.0
M
131
M
131
C
121
Benzyl2,3,6-trideoxy-2-fluoro-/3-~-g~lactopyr~noside 3-amino4.85 4.77 7.0 8.0 8.0 52.0 3-benzamido4.30-4.60-
3.15 4.0
3-(trifluoroacetamido)4.63 4.37 3.75 7.5 9.0 9.0 51.0
3.78 7.0
1.47
C
127
3.24
2.98 7.0
0.94
B
132
4.29
3.18 7.0
1.33
C
127
C
127
C
133
3.88 3.0
4-O-benzoyl-3-(trifluoroacetamido)-
4.71 4.57 4.49 5.52 3.90 1.24 7.0 10.0 3.0 7.0 5.0 8.0 54.0 Methyl 2,3,6-trideoxy-2-fluoro-~-galactopyranoside 3-amino-P4.36 4.17 3.02 3.62 3.68 1.35 7.6 9.5 3.0 1.0 6.5 3.3 51.0 13.0 3.0
-193.4
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
I25
TABLEXXIX (continued) Compound H-1 H-2
6F
References
H-3
H-4
H-5
J1.z
J2.3
53.4
J4.5
55.6
H-6 H-6' 5 5 , ~ 56.6
JFJ
JF.~
JFJ
JFP
JF,5
JF,6
3.82
4.32 7.0
1.32
C
132
5.65 1.0 2.0
4.05
1.27
c
133,137
3.81 3.0
3.9 6.4
1.26
A
131
3.81
3.90 6.4
1.26
C
133
3-benzamido-P4.50-
JF.6'
3-benzamido-4-O-benzoyI-p4.62 4.55 4.80 7.4 10.7 3.7 3.0 52.9 12.5 3-(trifluoroacetamido)a anomer 4.52 4.45 4.27 7.3 10.0 3.0 6.8 51.0 10.0 P anomer 4.55 4.46 4.30 7.4 10.4 3.1 0.5 50.7 13.5
1.1
3.1
6.4
S
b
"JJH-I, H-3) = 1.5 Hz. Ref. 137 reported couplings: J (H-I, H-2) = 10.5 andJ(H-2, H-3) = 8.0 Hz.
TABLEXXX 'H- and I9F-N.m.r. Data for Amino-2,3,6-trideoxy-2-fluorohexo-pyranosides, -pyranoses, and -pyranosyl Halides Compound H-1 H-2
H-6'
H-3
H-4
H-5 H-6
51.2
J2.3
J3,4
54,s
55.6
35.6
J64'
JFJ
JF,~
JFJ
JF,~
JF,S
JF.6
JF,~
SF
S
References
4-0-Benzoyl-2,3,6-tndeoxy-2-fluoro-3-(tnfluoroacetamido)-~~-gala~opyranosyl bromide 6.68 4.78 4.93 5.63 4.50 1.23 C 127 4.0 10.0 7.0 50.0
6-Azido-QO-benzoyl-2,3,6-tndeoxy-2-fluoro-~-ribo-hexopyranosyl halide chloride a anomer 6.25 4.86 2.31/2.66 5.11 4.31 3.36-3.62 C 3.8 12.0/5.0 11.Y5.0 10.0 5.0 3.0 48.0 p anomer 5.55 4.65 6.5 9.015.0 4.5 48.0
855.0
1.5
2.0/2.88 9.0/5.0 13315.0
5.16 8.0
4.00
3.36-3.62
C
138 a. b
138 o.e
1.0
(continued)
I26
RENE CSUK AND BRIGITTE I. GLANZER TABLEXXX (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6’
Jl.2
J2.3
53.4
J4,5
55.6
Js.6,
56,6’
JFJ
JF,Z
JF$
JF.4
JF,~
JF.6
JF.6,
4.65 11.Y4.7
2.32/2.64
4.28 5.0
2.7
47.5
8.3/5.0
5.14 10.0 1.4
3.94
2.20/2.57
5.16 11.5 1.4
4.05 5.0
2.7
6.61 3.8
7.05 4.0 2.0
a bromide
a iodide
11.5/5.0
11.Y5.0
11.Y5.0
6F
S
References
3.49 13.5
C
138
3.49 13.5
C
o.d
138 a.e
8.Y5.0 47.5 6-Azido-4-O-henzoyl-2,3,6-trideox~2-fluoro-~-ribo-hexopyranose a anomer
5.44 3.8 1.0
4.70 2.2Y2.59 5.02 4.30 3.31-3.50 -190.5 C 12.0/5.0 11.515.0 10.0 48.0 9.0/5.5 1.2 p anomer 4.93 4.40 1.91/2.81 5.02 3.88 3.31-3.50 -190.2 C 7.0 11.0/5.0 11.Y5.0 10.0 3.0 49.0 12.0/7.0 1.2 Methyl 6-~do-4-O-henzoyl-2,3,6-trideoxy-2-fluoro-~-~-ribo-hexopyranoside 4.10 4.11 1.47/2.35 4.71 C 7.2 10Y5.2 10Y5.0 3.5 48.0 12.Y7.0
138 a.f
138 a.g
138 ash
Shifts and couplings for axial (a) and equatorial (e) proton, respectively. J (H-3a. H-3e) = 11.5, J (H-I, H-3e) = 0.5 Hz. J ( H - ~ uH-3e) , = 13.5 Hz.d J (H-I, H-5) = 0.3, J (H-I, H-3e) = 1.3, J (H-3a, H-3e)= 11.5Hz.’J(H-l,H-3e) = 1.5Hz.’J(H-l,H-3e)=0.3;J(H-l,OH)= 3.5,J(H-3a,H-3e)= , = 12.0 Hz. 11.5 Hz. g J (H-I, OH) = 5.0, J (H-3a, H-3e) = 12.0 Hz. J ( H - ~ uH-3e) @
(138) T. Tsuchiya, Y.Takahashi, M. Endo, S.Umezawa, and H. Umezawa, J . Carbohydr. Chem., 4 (1985) 587-61 1.
TABLEXXXI ‘H- and 19F-N.m.r. Data for Fluorinated Unsaturated Amino Sugars Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6‘
Jl.2
JZS
J3.4
J4,s
55.6
55.6
J6.6
JF.1
JFJ
JFJ
JF.~
JF,5
Jp.6
JF,6’
6F
S
References
2,3,6-Trideoxy-2-fluoro-a-~-arabino-hex-5-enopyranoside
benzyl 3-azido4.67 4.62 3.11 4.0 7.0 3.5 11.0 47.0 12.5
3.94
4.66
4.44
C
127
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
127
TABLEXXXI (continued) Compound H-1 H-2
H-3
H-4
H-5
52.3
J3,4
54.5
55.6
H-6 55.6
H-6'
J1,Z
SF
JFJ
JFJ
JFJ
JF,~
JFJ
JF.6
JF.~
S
References
56,6
benzyl 3-benzamido5.10 4.81 5.18 4.90 B 4.74 4.25 132 1.0 2.5 8.0 45.0 methyl 3-benzamido4.92 4.75 4.68 4.92 4.92 132 C 1.0 3.5 44.0 methyl 3-benzamido-4-0-benzoyl132,133 5.03 4.86 5.24 5.98 4.97 4.83 C 2.0 4.0 4.8 1.5 137 8.0 46.0 8.0 3.3 methyl 4-O-benzoyl-3-(trifluoroacetamido)4.33 6.0 -193.7 c 131 1.7 3.3 3.7 7.3 47.0 7.3 1.7 Methyl 3-benzamido-2,3,4,6-tetradeoxy-2-fluoro-~-~-~~reo-hex-4-enopyranoside 4.84 4.66 4.77 I37 5.11 I .85 C 1.5 3.5 9.0 46.0 Methyl 2-benzamido-3-O-benzyl-2,4,6-trideoxy-6-fluoro-~-~-~~reo-hex-4-enopyr~oside -224.1 C I34 (1
48.0 " J (H-I, H-3)
=
48.0
1.5 Hz.
TABLEXXXII 'H- and IgF-N.m.r. Data for Fluorinated Aminodeoxyhexo-furanosesand -furanosides Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
Ji.2
52.3
534
54.5
55.6
Js,~
J6,6'
JF,I
JFJ
JF.~
JF,~
JF.S
JF,~
JF,~
3,6-Dideoxy-~~-galactofuranosyl fluoride 3-azido-5-0-benzoyl-2-0-benzyl5.83 3.95-4.605.40 6.4 59.3 3-azido-5-O-benzoyl-2-O-methyl5.74 3.95 3.78 4.24 5.36 3.0 6.2 4.2 6.2 60.0 10.5 1.8 ~
S
References
1.41
C
139
1.42
C
139
6F
(continued)
RENfi CSUK AND BRIGITTE I. GLANZER
128
TABLEXXXII (continued) Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6’
51.2
J2J
J3.4
54,s
55.6
55.6’
J6,6#
JFJ
JF,Z
JFJ
JFC
JF,S
JF.6
JF.~
SF
S
References
5-O-benzoyl-2-O-rnethyl-3-(trifluoroacetarnido)5.87 3.92 4.35-4.58 5.42 1.43 C I39 4.0 7.0 60.0 7.0 5-O-benzoyl-2-O-benzyI-3-(tri~uoroacetarnido)5.83 4.04 4.52 4.37 5.39 1.42 C 139 1.O 4.8 2.0 6.6 59.4 7.2 3-Acetamido-2,3,5,6-tetradeoxy-5-luoro-l-O-(4-nitrobenzoyl)-~,~-~~-~~~o-hexofuranose 6.65 2.212.7 4.7 4.13 4.75 1.43 C 140 4.9 8.0 2.0 2.7 6.6 b 24.6 48.7 23.9 Methyl 3-acetamido-2,3,5,6-tetradeoxy-5-luoro-~~~-ri~o-hexofuranoside 5.14 1.7-2.3 4.55 3.86 4.71 1.34 C 140 2.0 3.0 6.4 24.2 24.7 56.0 (1
a
’
J (N-H, H-3) = 9.0 Hz. J (H-2, H-2’) = 14.1 Hz.
(139) A. Hasegawa, M. Goto, and M. Kiso, J . Carbohydr. Chem., 4 (1985)627-638. (140) J. T. Welch, B. M. Svahn, S . Eswarakrishnan, J. P. Hutchinson, and J. Zubieta, Carbohydr. Res., 132 (1984)221-231. TABLEXXXIII ‘H- and IgF-N.m.r. Data for Fluorinated Aminodeoxypentopyranosides Compound H-1 H-2
H-3
H-4
H-5
H-5’
Ji.2
JZJ
J3.4
J4,5
54.5’
Js,s*
JFJ
JFJ
JFJ
JF,~
JF.S
JF,s’
6F
S
Methyl 4-~-~yl-2-amino-2,3-dideoxy-3-fluoro-~~-arabinopyranoside 4.80 3.25 4.65 -198.9 C 3.9 10.0 3.9 10.0 49.1 Methyl 2-amino-2,3,4-trideoxy-3.luoro-f~reo-pentopyranoside (Y-L4.75 2.8 4.5 -187.7 C
3.7 3.7
9.3 11.7
References
129
129 a
51.3
14.117.5
p-D-
4.0 7.3
2.85 9.0 12.0
4.45 9.016.0 50.5
Couplings for the axial and equatorial proton, respectively.
-186.0
C
129 n
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
IH-
TABLEXXXIV and I9F-N.m.r. Data for 2-deoxy-2-halogeno-hexopyranosyl Fluorides
3,4,6-Tri-0-acetyl-2-deoxy-~-galactopyranosyl fluoride 2-bromoa anomer 50.5 25.1 p anomer 10.0 49.7 2-iodoa anomer 50.0
8.0 9.0 50.3 10.0 2-chloroa anomer
34,141
- 135.6
34
-139.4
34
-130.8
34
- 144.9
34,40, 141,142, 143,"
- 136.0
15.34, 40
3.94
- 147.6
40,144
3.47
- 138.9
40,144
- 139.8
34,40, 142,143
24.0
p anomer
51.0 10.6 2-iodoa anomer
2.4 50.5
- 145.0
27.6
p anomer
49.8 10.2 3,4,6-Tri-0-acetyl-2-deoxy-~-glucopyranosyl fluoride 2-bromoa anomer 5.8 2.5 9.0 9.0 9.0 51.5 25.2 /3 anomer
51.2
I29
11.0 27.8
b
(continued)
RENB CSUK AND BRIGITTE
I30
I. GLANZER
TABLEXXXIV (continued)
49.9 9.3 3,4,6-Tri-0-acetyl-2-deoxy-~-mannopyranosylfluoride 2-bromoa anomer
1.5 50.2
4.0 2.8 p anomer 5.95 I .8 52.0 2-chloroa anomer
C
14,15 34,40 141.143'
C
142,145
-127.8
B
40,144
-118.6
C
144
-116.9
A
34,40, 141,143
-123.2
9.5
3.92 3.6 49.5 2.0 p anomer 49.4 3.6 2-iodoa anomer
I .5
4.3 51.7 *3.9 p anomer 5.95 I .8 52.0
9.5
d
142
3,4,6-Tri-0-acetyl-2-deoxy-~-talopyranosyl fluoride 2-bromo-a-
-121.4
C
34
-114.6
C
34
49.8 4.6 2-iodo-a50.5
6.3
nJ(H-1,H-3)=0.4Hz.bJ(H-I,H-3)=0.2,J(H-l,H-5)=0.2Hz.LJ(H-2,H-4)=0.3Hz.dRef.
reported 4.3 Hz,whereas Ref. 141 reported 1.0 Hz,in addition: J (H-I, H-3)= 0.5,J (H-2, H-4)= 0.5, J (H-1, H-5)= 0.2 Hz.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
131
(141) J. C. Campbell, R. A. Dwek, P. W. Kent, and C. K. Prout, Carbohydr. Res., 10 (1969) 71-77. (142) K. R. Wood, P. W. Kent, and D. Fisher, J . Chem. Soc., C , (1966) 912-915. (143) L. D. Hall and J. F. Manville, Carbohydr. Res., 8 (1968) 295-307. (144) L. D. Hall and J. F. Manville, Can. J. Chem., 47 (1969) 379-385. (145) J. C. Campbell, R. A. Dwek, P. W. Kent, and C. K. Prout, Chern. Commun., (1968) 34-35.
TABLEXXXV 'H- and IgF-N.m.r. Data for 2-Deoxyhexopyranosyl Fluorides and 2,3-Dideoxy-2-fluoro-hexopyranosides Compound H-1
H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
JZJ
53,4
54,s
55.6
55.6
56.6'
JF,I
JF.Z
JFS
JF,~
JF,S
JF,~
JF,~
4.34 4.5
4.09 -131.1 12.8
2-Deoxy-~-arabino-hexopyranosyl fluoride 3,4,6-tri-O-acetyla anomer 5.76 2.43/1.86~ 5.32 5.08 4.14 1.6/2.850 5.2/10.8 9.5 2.0 51.2 5.0/38.0 9.5 p anorner
6F
S References
C
14,15, 33,34,40 n.6
-125.2
c
40 (I
15.3d10.7e 3,4,6-tri-O-benzoyl-a5.82 2.7512.07~ 5.72 1.5/2.5a 51.1 5.3/38.3 2-Deoxy-D-lyxo-hexopyranosyl fluoride 3,4,6-tri-O-benzoyl-a6.01 2.80/2.0a 5.76 6.00 2.0/2.5a 11 3 6 . 0 1.0 3.0 51.0 3,6-di-O-benzoyl-a5.88 2.0-3.0 5.50 2.0/2.0 11.5/5.5 3.0 52.0 4,6-di-O-benzoyl-a5.93 1.8-2.7 4.2-4.7 5.68 2.012.0 3.0 1.0 52.0
-
4.57
-
-130.1
C
33 a.c
4.75 6.0
4.10-4.70 6.0
4.2-4.8
-
C
I46 n.6
C
146 a
-
4.2-4.7
-
C
146
(continued)
TABLEXXXV (continued) Compound
H-1
H-2
H-3
H-4
H-5
H-6
H-6'
Ji.2
52s
53.4
54.5
55.6
55.6'
56.6'
JFJ
JF,Z
JF.3
JF.4
JF,~
JF,6
JF,~
Methyl 2-deoxy-2-fluoro-~-o-ribo-hexopyranoside 4,6-0- benzylidene-3-deoxy4.10 4.25 1.74/2.3e 2.93 3.05 3.40 7.5 11.3/5.5e 11.5/4.0e 9.0 10.0 4.7 3.5 49.0 11.5a/5.0e 1.5
S References
6F
C
4.09 10.0
The symbol e stands for equatorial, and a for axial. J (H-2e, H-2a) 13.5 Hz." J (H-3a, H-3e) = 11.5 Hz.
138 4.d
=
13.9 Hz. J (H-2e, H-2a)
=
(146) I. Lundt and C. Pedersen, Acta Chem. Scand., 25 (1971) 2749-2756.
TABLEXXXVI
'H-and 'gF-N.m.r. Data for Fluorinated 6-Deoxyhexopyranose Derivatives Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
51.2
52.5
53.4
J4.5
556
Js.6
36,6
JFJ
JF,Z
JF,~
JF,~
JFJ
JF.~
JF,~
2,3,4-Tri-0-acetyl-6-deoxy.cu-~-mannopyranosyl fluoride 5.45
5.00
-
5.32
49.0
3.96 6.0
1.2
6F
S
-119.8
C
150
-208.3
D
147,148
-208.0
D
147,148
-209.9
C
148
-209.9
C
148 *
-197.0
D
149
References
2,6-Dideoxy-2-fluoro-~-galactopyranose a anomer
0.5
49.4
p anomer
13.0
3.5 51.0 14.5 1,3,4-tri-O-acetyl-P6.42 5.39 4.0 10.5 3.5 0.5 49.5 11.5
4.0
4.0 5.33 6.5 3.8
Trifluoromethyl3,4-di-0-acetyl-2,6-dideoxy-cu-~-galactopyranoside 3.9 9.5 3.5 2.0 6.6 0.2 48.5 13.0 3.5 2,6-Dideoxy-2-fluoro-~-glucopyranose a anomer 2.5
50.5
16.0 (continued) 132
TABLEXXXVI (continued)
p anomer -197.2
D
149
C
149
C
149
C
149
0.1 49.5 14.5 1,3,4-tri-O-acetyla anomer
8.0 3.5 4.0 0.5
p
9.5 51.5 anomer
9.5 14.5
9.5
6.5
9.5 49.0
9.5 12.5
9.5
6.5
Trilluoromethyl 3,4-di-O-acetyl-n-~-glucopyranoside 4.0 0.5
9.5 48.0
9.5 12.0
9.5
6.2
b
2,6-Dideoxy-2-fluoro-~-mannopyranose a anomer
20.1 51.0 p anomer
-202.7
D
149
-221.2
D
149
C
149
C
149
30.0
8.0 49.5 30.5 1,3,4-tri-O-acetyl-a7.5
49.0
30.0
Trifluoromethyl3,4-di-O-acetyl-2,6-dideoxy-/3-~-mannopyranoside 0.5 17.0
2.2 50.5
9.8 30.0
8.5 2.0
-220.8 6.2
“ J (OCF,,F) = 1.25 Hz.* J (OCF,,F) = 0.8 HZ.
(147) W. Korytnyk, S. Valentekovic-Honvath, and C. R. Petrie, 111, Tetrahedron, 38 (1982) 2547-2550. (148) C. G. Butchard and P. W. Kent, Tetrahedron, 35 (1979) 2551-2554. (149) G. C. Butchard and P. W. Kent, Tetrahedron, 35 (1979) 2439-2443. (150) Y. V. Voznyi, Bioorg. Khim., 7 (1981) 239-241.
I33
R E N k CSUK AND BRIGITTE I. GLANZER
134
TABLEXXXVII 'H- and lPF-N.m.r. Data for Fluorinated Hex-L(or 3)-enopyranose Derivatives Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
52.3
J3.4
J4.5
J5.6
Js.6,
J6,6
JFJ
JFJ
JFJ
JF,~
JFC
JF,~
JF,~
3-Deoxy-cu-~-erytlrro-hex-2-enopyranosyl fluoride 2,4,6-tn-O-acetyl5.70 5.90 5.40 4.10 4.30 2.0 8.5 56.0 2,4,6-tn-O-benzoyl4.90 6.00 6.25 6.05 4.50 2.0 9.0 56.0 3,4-Dideoxy-~-glycero-hex-3-enopyranosyl fluoride 6-0-acetyl-2-dose a! anomer 5.57 6.29 7.10 4.97 4.40 4.32 10.4 1.7 5.0 5.0 11.8 51.2 5.9 /3 anomer 5.58 6.35 7.18 4.83 4.1-4.6 10.7 3.2 52.0 4.8 6-0-benzoyl-2-dose a! anomer 5.57 6.28 7.12 5.05 4.61 4.55 10.4 1.6 4.8 4.8 12.0 51.0 5.9 p anomer 5.58 6.36 7.13 4.90 4.00-4 S O 10.5 3.0 52.0 4.6 2,3,6-Trideoxy-6-fluoro-cu-~-erythro-hex-2-enopyranoside ethyl 4-0-acetyl5.06 5.85 5.27 4.1-4.40 4.53 2.5 9.6 48.0 48.0 methyl 4-0-acetyl5.00 5.95 5.32 3.75-4.40 4.59 10.2 48.0 48.0 " J (H-I, H-3) H-5) = 2.0 Hz.
=
'
0.7, J (H-3, H-5) = 2.4 Hz. J (H-3, H-5)
=
6F
-141.6
S
References
C
151
C
151
C
151,152 Y
-118.6
C
152 b
-135.2
C
151,152 c
-118.2
C
152
A
153
A
153
2.0 Hz. J (H-1, H-3) = 0.8, J (H-3,
(151) K. Bock and C. Pedersen, Tetrahedron Lerr., (1969) 2983-2986. (152) K. Bock and C. Pedersen, Acra Chem. Scand., 25 (1971) 1021-1030. (153) G. Descotes, J. C. Martin, and Tachi-Dung, Carbohydr. Res., 62 (1978) 61-71.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
135
TABLEXXXVIII 'H- and I9F-N.m.r. Data for Miscellaneous Fluorinated Hexopyranoside Derivatives
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
Ji.2
J2.3
J3,4
54,s
55.6
5 5 , ~
5 6 , ~
JFJ
JFJ
JF.~
JF,~
JFd
JF.6
JF.6'
SF
S
References
Methyl 4-O-benzoyl-6-bromo-2,3,6-trideoxy-2-fluoro-~-~-r~~~-hexopyranoside 4.54 4.45 1.9312.76e 5.02 3.89 3.47 3.60 C 7.5 11.0/5.0 11.0 48.0 Ethyl 4-0-acetyl-2,3,6-trideoxy-6-fluoro-cu-~-e~thro-hexopyranoside 4.4-4.9 1.68-1.85 4.4-4.9 3.3-4.05 4.45 A 48.0 48.0 Ethyl 4-0-benzyl-2,3,6-trideoxy-6-fluoro-cu-~-e~th~o-hex-2-enopyranoside 6.04 5.67 3.30-4.30 4.57 -233.2 2.4 2.4 48.0 48.0
" J (H-30, H-3e) =
138 a
1.53
C
1 I7
11.O Hz.
TABLEXXXIX 'H- and I9F-N.m.r. Data for 2-Deoxy-2-halogenopentopyranosyl Fluorides
Compound H-1 H-2
H-3
H-4
H-5
H-5'
JIJ
J2.3
53.4
54,s
54.5'
JSd*
JFJ
JFJ
JFJ
JF,~
JFS
JF,I'
SF
S
References
C
141
-126.4
C
34
-121.6
C
34
-126.7
C
34
2-Deoxy-~-arabhopyranosylfluoride 2-bromo-P51.2 25.8 3,4-di-O-acetyl-2-bromo-a-
50.5
3.5
3,4-di-O-acetyl-2-iodo-a50.0
5.0
3,4-Di-O-acetyl-2-deoxy-~-lyxopyranosyl fluoride 2-bromoa anomer
50.1
3.5 (continued)
RENB CSUK AND BRIGITTE
136
I. GLANZER
TABLEXXXIX (confinued) Compound H-1 H-2
H-3
H-4
H-5
H-5'
51.2
52.3
J3c
J4.s
54,s
Js,~
JFJ
JFJ
JFJ
JF,~
JF,S
JFF
SF
S
References
p anorner -144.1
34 a
50.8 26.8 2-iodoa anorner -120.4
34
-141.1
34
50.0 3.5 p anomer a
50.8
29.0
3,4-Di-O-acetyl-2-deoxy-~-nbopyranosyl fluoride 2-brornoa anomer 51.3
- 147.6
34
-127.9
34
-141.9
34
- 123.9
34
- 146.5
34
25.1
p anomer
50.4 3.4 2-iodoa anomer 50.7
51.0
27.6
p anorner 6.5
3,4-Di-O-acetyl-2-deox~~-xylopyranosylfluoride
2-bromoa anorner
b
50.3
25.1 p anorner - 128.0
51.0
34
9.0 (continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
137
TABLEXXXIX (continued) Compound H-1 H-2
H-3
H-4
H-5
H-5'
11.2
32.3
53.4
54.5
54,s
J5.5'
JF,l
JF,Z
JFS
JF.4
JFJ
JFJ'
SF
S
References
-138.0
C
34
2-iodo(x anomer b
50.8
29.0 p anomer
C
-122.5 51.1
34
9.2
May have to be reversed with
I Y - D - X Y ~ . I,
May have to be reversed with P-D-~Yxo.
TABLEXL 'H- and I9F-N.m.r. Data for 2-DeoxypentopyranosylFluorides Compound H-1
H-2
H-3
H-4
H-5
H-5'
Ji,2
J2.3
J3,4
54,s
543
J5,S
JFJ
JF,~
JFS
JF,~
JF.S
JF.S
SF
S
References
3,4-Di-0-benzoyl-2-deoxy-~-erythro-pentopyranosyl fluoride a anomer 5.70 2.1-2.6 2.0/3.0a 51.0 p anomer 5.53 1.7-2.4 2.112.1 11.0d6.0e 51.0
5.75 3.0
5.45 10.2
4.45 5.2
3.98 11.2
C
154
5.57 3.0
5.50 2.0
3.70 1.0
3.80 13.0
B
154
4.18 10.6
C
4.05 12.5
C
3,4-Di-O-benzoyl-~-threo-pentopyranosyl fluoride a anomer 5.77 2 . 6 Y 2 . 1 0 ~ 5.75 5.46 4.00 2.6/1.8e 50.7 p anomer 5.77 3.2/3.2e
5.0110.8
9.2
10.0
5.5
5.41
5.22 3.0
4.54
0.6
I54 ax
5.0/36.4 2.2-2.8 3.2e
2.5
154 U.d
51.0
" The symbol a stands for axial, and e for equatorial.
Hz. ,I J (H-20, H-2e)
= 15.0 Hz.
J (H-20, H-2e) = 13.0. J (H-2a, H-2e) = 13.8
(154) K. Bock and C. Pedersen, Acta Chem. Scand., 25 (1971) 2757-2764.
RENk CSUK AND BRIGITTE I. GLANZER
138
TABLEXLI 'H- and 'PF-N.m.r.Data for Fluorinated DeoxypentofuranoseDerivatives Compound H-1 H-2
H-3
H-4
H-5
H-5'
51.1
J2,3
J3,4
54,s
J4.59
Js,r
6F
S
References
JFJ
JF,Z
JFS
JFA
JFJ
JFJ'
-106.5
C
155
-103.2
C
155
-
C
108
-
N
I10
3,5.Di-O-benzoyl-2-bromo-2-deoxy-~-pentof11ranosy1 fluoride a-D-arabino6.07 4.44 0.8 3.0 61.0 7.9 p-D-XY/O-
6.03
4.42
5.66
4.60
4.90
5.85
5.14 4.71 5.8 5.8 65.0 6.0 6.0 2-Deo~y-2-fluoro-cu-D-~rabinofuranosyl bromide 3-0-acetyl-5-0-benzoyl6.45 5.34 5.18 4.60 0.0 12.0 50.0 23.0 3,5-di-0-benzoyl6.67 5.6 5.5 4.75
4.71
5.0
50.0
(155) K. Bock, C. Pedersen, and P. Rasmussen, Acla Chem. Scand., Ser. B , 29 (1975) 185- 190.
TABLEXLII lH- and "F-N.m.r. Data for 3-C-Branched 3-Fluoro-~-glucofuranoses Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
51.2
52.3
J3,4
J4,s
J5,6
J5.6
56,6
JFJ
JF,Z
JFS
JF,~
JF.~
JF,~
JF,~
3-Deoxy-3-fluoro-~-glucofuranose 3-C-(acetoxymethyl)1,2-O-isopropylidene-a5.88 4.63 3.76 4.0
-
4.15
S
References
C
156 Y
11.0
(continued)
I39
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLEXLII (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JLZ
J2.3
53.4
J4.5
J5,6
J5.6
J6.6
JFJ
JF,~
JF.~
JF,~
JF,S
JF.6
JF,~
1.2: 5,6-di-O-isopropylidene-a5.88 4.63 3.70 4.0 11.0 6-0-benzoyl1,2-0-isopropylidene-a5.91 4.64 4.55 3.85 3.8 8.0 10.0 25.0 3-C-(ethoxyallyl)1,2-0-isopropylidene-a6.06 4.82 4.10-4.40
-
4.30
S
References
C
156 b
-
4.32
C
156 c
C
157
3.99
C
157
4.06
C
157
C
157
C
157
C
157
C
157
C
157
3.74-3.92
4.0
11.0
I ,2 :5,6-di-O-isopropylidene-a-
6.03 4.0
4.92 14.5
4.75 8.0 27.0
4.21
-
3-C-[(ethoxycarbonyl)(formylirnino)methyl]-1,2: 5.6-
di-0-isopropylidene-a6.02 4.94 4.0 13.0
4.88 6.0 27.0
4.4 6.0
-
3-C-[ethoxy(ethoxycarbonyl)(formylamino)methyl]-1,2: 5,6di-0-isopropylidene-a5.82 4.67 4.89 2.50 3.82 3.5 6.5 14.5 27.5 3-C-(hydroxymethyl)I ,2: 5,6-di-O-isopropylidene-a5.90 4.67 3.60 4.50 4.0 12.0 1,2-0-isopropylidene-a5.90 4.58 3.60 4.20 4.0 12.0 3-C-[ 1,2-di(hydroxyethyl)l-1,2 :5,6-di-O-isopropylidene-a5.88 4.69 3.80 4.60 4.0 12.0 I ,2-O-isopropylidene-3-C-(methoxyallyl)-a6.07 4.83 4.30-4.67 4.16 4.16 3.5 12.0
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
I40
TABLEXLII (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6’
Jt,t
52.3
53,4
54,s
55.6
55.6’
56,6
JFJ
JF,~
Jp.3
JF.~
JFJ
JF,~
JF,~’
I ,2: 5,6-di-O-isopropylidene-3-C-(methoxycarbonyl)-a5.99 4.68 4.64 4.00 4.40 4.0 8.0 15.0 26.0
S
References
C
157
“ J (H-l’, H-1‘3 = 13, J (H-l’, F) = 14 Hz, J (H-I”, F) = 34 Hz; (H-1‘) = 4.84 p.p.m.; (H-1”) = 4.27 p.p.m. J(H-1’. F) = 13 Hz;J(H-I”, F) = 34 Hz;J(H-I’, H-I”) = 13 Hz; (H-1’) = 4.70p.p.m.; (H-1’7 = 4.24 p.p.m. J (H-l’, H-I”) = 13 Hz; J (H-1’, F) = 14 Hz; J (H-I”, F) = 34 Hz; (H-1’) = 4.84 p.p.m.; (H-1’3 = 4.29 p.p.m. L.
(156) A. J. Brink, 0. G. De Villiers, and A. Jordaan, Carbohydr. Res., 54 (1977)285-291. (157) K.Bischofberger, A. J. Brink, and A. Jordaan, J . Chem. Soc., Perkin Trans. I , (1975)2457-2460. TABLEXLIII ‘H- and I9F-N.m.r. Data for 3-Deoxy-J-C-(monoor di)tluoromethylene-D-hexo(or pento)furanoses
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6’
Jt,2
52.3
53,4
54.5
55.6
55,6’
56,6’
JF,I
JFZ
JF,~
JF,~
JFS
JF.6
JF.6’
SF
S
References
3-Deoxy-3-C-(fluoromethylene)-1,2 :5,6-di-O-isopropylidene-cu-~-hexofuranose ribo-
(2)isomer 5.90 5.06
4.3 1.5
1.4
1.0
( E ) isomer 5.82 5.36 4.0 1.3 0.0 1.3 xylo-
(Z)isomer 5.84 4.93 3.7 0.3 0.3 1.7 (E) isomer 5.81 5.28 3.7 1.0 0.0
1.0
3.36 6.6 1.9
4.00 6.6 0.9
3.76 8.4 0.9
-202.9
4.63 7.6
3.84
-
4.14
-198.5
82.5
5.5
1.8 82.9
4.87 8.3 2.3
4.42 6.0
1.2 82.0
4.67 6.5 1.7
2.1 82.0 2.0
5.12 3.2 1.0
C
37 a
C
37 b
3.78 8.3 1.6
-205.8
0.5
4.00 7.2 0.7
4.42 6.5
4.04 7.1
3.78 8.1
-201.9
0
0
0.5
C
37 c
C
37 d
(continued)
141
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLEXLIII (continued) Compound H-1 H-2 J1.2
J2,3
JF,l
JFJ
H-3
H-4
H-5
H-6
H-6'
J3.4
54,s
554
55.6'
56,6'
JF,~
JFJ
JF,~
JF.~
6F
S
References
3-Deoxy-3-C-(difluoromethylene)-l,2 :5,6-di-0-isopropylidene-cu-o-hexofuranose ribo5.87 4.4 1.4 90.0 xylo5.91 4.0 f0.5 8
5.22 2.6 1.2 5.22
1.0 1 .o
4.86 4.5 3.0 3.0
4.14 6.2 1.0
4.0
3.79 8.0
-247.1 -243.4
C
37
5.5
4.77 7.9 2.8
4.47 6.2 0.5
4.05 7.0 0.2
3.78 8.4 1.7
-244.1 -241.5
C
37
1.o
h
3-Deoxy-3-C-(difluoromethylene)-l,2-0-isopropylidene-(~-o-furanose ribo-hexo5.91 5.28 4.96 3.2 4.3 4.0 1.5 3.2 I 2.8 3.2 erythro-pentodialdo- 1 ,4-furanose 6.04 5.29 5.16 4.1 2.1 '1.0 0.9 3.6 g 2.0 4.0
3.90 2.5 1.2
3.50-3.75 8.5
9.45
-244.4 -241.0
C
158
-245.3 -244.0
C
I58 J
2.1
* (H-3') = 6.83 p.p.rn.; J (H-2, H-4) = 1.4 Hz. (H-3') = 7.01 p,p.rn.; J (H-2, H-4) = 1.3 Hz. (H-3') = 6.82 p.p.m. (H-3') = 6.74 p.p.m. J (H-2, H-4) = 1.2 Hz; J (F, F) = 38 Hz. f Couplings to rrans-oriented fluorine. Y Couplings to cis-oriented fluorine. * J (F, F) = 35.5 Hz. ' J (H-2, H-4)= 1.0 Hz; J (F, F) = 40.8 Hz. J (H-2, H-4) = 1.2 Hz; J (F, F) = 33.8 Hz. J
(158) J. M. J. Tronchet, B. Gentile, J. Ojha-Poncet, G. Moret, D. Schwarzenbach, F. Barbalat-Rey, and J. Tronchet, Carbohydr. Res., 59 (1977) 87-93.
TABLEXLIV 'H- and 'gF-N.m.r. Data for Fluorinated C(or O)-Branched o-Pentopyranose Derivatives Compound H-1 H-2
H-3
H-4
H-5
J1.z
J2,3
J3,4
54.5
54,s'
H-5' Jss,
JF,I
JF,~
JF.~
Jp.4
JF,~
JF,Y
S
1,2-Di-0-acetyl-5-0-benzoyl-2-deoxy-2-fluoro-3-0-formyl-o-arab~ofuranose (Y anomer 6.36 5.71 4.12 4.98 C
References
156
5.5 16.0
(continued)
RENB CSUK AND BRIGITTE I. GLANZER
142
TABLEXLIV (continued) Compound H-1 H-2
H-3
H-4
52.3
53.4
54,5
H-5 54,5'
H-5'
Ji,z
5
References
JFJ
JFJ
JFJ
JF.~
JFJ
JFS,
4.70
C
156
4.70
C
157
4.70
C
156
4.60
C
156
J5.5,
p anomer 6.44
5.35 4.35 3 .O 10.0 21.0 3 4 4Acetoxyrnethyl)-3-deoxy-3-fluoro-~-xylofuranose 5-0-acetyl- 1,2-O-isopropylidene-a5.98 4.64 4.00 4.0 12.0 1.2,5-tri-O-acetyla anomer 6.50 5.46 4.00 5.0
24.0
p anomer
6.10
-
4.10
5.34
14.0
3-Deoxy-3-fluoro-l,2-O-isopropylidene-cu.~-xylofuranose 3-C-(hydroxymethyl)5.92 4.58 4.0 12.0 3-C-(ethoxyallyl)5.95 4.68 4.0 12.0
3.60
-
4.40
C
157
4.30
-
3.81
C
157
5.0
TABLEXLV 'H- and I9F-N.m.r. Data for Miscellaneous, Fluorinated Branched Monosaccharides Compound H-1 H-2
H-3
H-4
H-5
&,a
J3.4
J4.5
J5.6
H-6 55,~
H-6'
JI,~ JF.1
JFJ
JF,~
JF,~
JFS
Jp.6
JF,~'
6F
S
References
56,6'
5(R)-5-C-Acetoxy-6-deoxy-6-fluoro-l,2 :3,4-di-O-isopropylidene-~-~-arabino-hexo-l,5pyranosd-dose 5.55 4.13 0.0 3.9
4.52l' 6.2
4.62"
4.69 46.0
5.13 9.6 46.8
-236.0
C
48
(continued)
N .M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
143
TABLEXLV (continued) ~~______
Compound H-1 H-2 J1t
4
3
JF,l
JF.2
H-3
H-4
H-5
H-6
H-6'
J3.4
J4.5
55.6
55.6'
56.6'
JFS
JF,~
JF.5
JF.6
JF.6'
SF
S
References
~~~
l-O-Acetyl-2,3,5,64etra-O-benzoyl-4-deoxy-4-fluoro-~~-hexofuranose galacto6.56 5.82 6.11 C 159 2.2 4.7 0.0 15.2 4.0 gluco6.69 5.47 5.88 6.10 5.02 4.72 C 159 0.0 0.0 0.0 0.0 7.3 5(S)-5-C-Acetoxy-3,5-O-benzylidene-6-deoxy~0uoro-l,2-O-isopr~pylidenea-D-xylo-hexo1,4-furanosd-dose 6.02 4.66 4.23" 4.62" 4.90 5.13 -240.2 C 48 3.4 0.0 0.0 9.7 45.1 46.7 2,~,4-Tri-~-acetyl-2-fluoro-~-~-ribopyranosyl fluoride 6.47 5.31-5.61 4.22 3.83 -153.0 C 98 2.0 1.5 13.0 -133.0 51.0 0.0 1.5 Trifluorometbyl 2,3,4-tri-0-acetyl-2-fluoro-/3-~-ribopyranos~de 6.44 5.58 5.44 4.26 3.86 -133.0 C 98 4.0 2.5 2.5 13.5 6.5 1.2 1-0-Acetyl-2,3,5-trii-O-benzoyl-4-fluoropentofuranose a-L-lyxo-
6.66 3.0 0.0
5.91 5.1 0.8
6.19
4.85
4.65
C
159
17.3
P-D-ribo-
6.61 5.78 6.00 4.78 5.53 C 159 0.0 5.3 8.0 1.0 3.9 4-0-Acetyl-5-deoxy-5-fluoro-1,2-O-isopropylidene-3-O-tosyl-~-~-~~reo-pento-l,4-furanos-4dose 6.08 4.83 5.28 4.48 4.73 -236.1 C 48 3.8 45.7 46.4 a
The assignments may have to be reversed.
(159) R. J. Ferrier and S. R. Haines, J . Chem. SOC.,Perkin Trans. 1 , (1984) 1675-1681.
RENk CSUK AND BRIGITTE I. GLANZER
I44
TABLEXLVI lH- and lgF-N.m.r. Data for Fluorinated Ketopyranose Derivatives Compound H-1 H-1' J3,4 J1.r JF,I
JF,V
H-3
H-4
J4,s
55.6
H-5 55.6
56.6'
H-6
JFJ
JF.~
J F ~
JF,~
H-6'
6F
S
References
C
160
D
161
C
162
JF,~'
l-Deoxy-l-fluoro-2,3 :4,5-di-O-isopropylidene-~-fructopyranose 4.37 4.37 4.25 4.64 4.39 3.74 3.92 -230.1 10.0 8.0 3.0 2.0 12.0 48.0 48.0 1.5 4-Deoxy-4-fluoro-~~-fructopyranose 3.72 3.56 4.06 4.78 4.26 4.03 3.75 11.8 9.75 3.5 1.6 2.0 13.0 1.8 12.9 49.0 6.5 1.3 7.8 4-Deoxy-4-fluoro-1,2-O-~sopropylidene-~-~-sorbopyranose -195.6 5.0 3.0 9.0 46.0 9.0
(160) P. J. Card and W. D. Hitz, J . Am. Chem. Soc., 106 (1984) 53484350. (161) M. BudMnsk$, M. Cern$, J. Dole2alovB, M. Kulhhnek, J. Pacak, and M. Tadra, Collect. Czech, Chem. Commun., 49 (1984) 267-274. (162) M. Sarel-Imber and E. D. Bergmann, Carbohydr. Res., 27 (1973) 73-77.
TABLEXLVII 'H- and '9F-N.m.r. Data for Mono- and Di-fluorinated Ketofuranose Derivatives Compound H-1 H-1'
H-3
H-4
H-5
H-6
54.5
55,6
Js,~
56.6
H-6'
JIJ*
53.4
'JFJ
JFJ
JF,3
JF.4
JF,S
JF,6
JF,~
"JFJ
JFJ-
JFJ
JF,~
JF.5
JF,6
JF,~
SF
S
References
1,3,4,6-Tetra-O-ace~l-~-fructofuranosyl fluoride a anomer 4.2-4.5 1.0
p anomer 4.2-4.5 7.0
5.55 5.0 7.0
5.00
5.4-5.7
A.2-4.5-
C
163
d.2-4.5-
C
163
16.0 6-O-Benzoyl-l-deoxy-l-flnoro-2,3-O-isopropylidene-~-~-f~ctofuranose 4.38-4.6 1 -225.2 C
164 b
47.7 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
145
TABLEXLVII (continued)
Methyl 3,4,6-tri-O-benzoyl-l-deoxy-l-fluoro-~-fructofuranoside a anomer 4.68 4.39 5.81 5.60 4 . 4 1 - 4 . 1 7 -230.8 B 164,165 b 2.2 4.9 46.9 p anomer 4.68 4.39 5.81 6.12 -232.3 C-B 164, 6.5 5.5 165” 46.9 6-Deoxy-6-fluoro-2,3-O-isopropylidene-l-O-~tolylsu~onyl-~-~-f~ctofuranose 164,” 4.05-4.95 -226.8 C 18.1
46.2
1,6-Dideoxy-l,6-di~uoro-2,3-O-isopropylidene-~-~-fructofuranose 4.52
4.57
5.0
47.1
5.0 17.7
C
164, 166,”
-233.1 -230.3
C
164, 165,”
-230.9 -234.8
C-B
164, 165,”
-225.0 -225.5
46.4
Methyl 3,4-di-0-acetyl-1,6-dideoxy-1,6-d~uoro-~-fructofuranoside a anomer 4.31
4.31 2.2
5.61 6.4
5.19 3.5
3.94 3.5
4.36
46.4 22.0
p anomer 4.42 9.6 46.6
4.26 1.3
5.19 7.1
5.64 5.0
3.90 2.4 22.3
41.3 4.2-4.34 10.5 46.9
“ The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. 6F values were taken from Refs. 164 and 165; although no standard was reported, C6F6 had obviously been used. (163) B. Erbing and B. Lindberg, Acta Chem. Scand., Ser. B , 30 (1976) 12-14. (164) R. D. Guthrie, I. D. Jenkins, and R. Yamasaki, Ausf.J . Chem., 35 (1982) 1003-1018. (165) R. D. Guthrie, I. D. Jenkins, and R. Yamasaki, Ausf.J . Chem., 35 (1982) 1019-1029. (166) J. Pacirk, J. HalaSkovir, V. Stepirn, and M. Cvernq, Collecf. Czech. Chem. Commun.,37 (1972) 3646-3651.
RENh CSUK AND BRIGITTE I. GLANZER
I46
TABLEXLVIII 'H- and "F-N.m.r. Data for 2-Deoxy-2-fluorohexopyranosylFluorides Compound H-1 H-2
&'I
H-3
H-4
H-5
H-6
H-6'
J1.t
Ja.3
53.4
54.5
55.6
J5,6'
J6.6'
YF.1
JFJ JFZ
JF,~ JF,~
JF,~
JF,~
JF,~ JF.~
J F , ~ J(F,F)
JF,~ J F ~
'JF,~
m
S
a
References
JF,~
2-Deoxy-2-fluoro-D-gdactopyranosy~ fluoride a anomer 54.3
24.5 48.9 14.6 3,4,6-tri-O-acetyla anomer 5.76 4.68 5.34 2.7 9.7 3.2 52.5 23.0 0.9 48.0 11.0 p anomer
4.9 5.48
4. 5
4. 5
4.06
1.0
3.5
52.5 14.3 5.0 51.3 14.8 2.5 2-Deoxy-2-fluoro-~-glucopyranosylfluoride (Y anomer 54.1 23.8 0.0 47.7 13.8 3,4,6-tri-O-acetyla anomer 5.80 4.54 5.54 2.9 9.6 9.5 53.3 23.8 0.5 0.0 48.3 12.3 p anomer 5.41 4.46 5.32 6.1 7.9 8.9 51.7 11.2 1.0 4.0 49.0 15.0
5.10 9.5 0.0 5.10 9.0
4.06
0.0
0.0 0.0
3.11 9.9
2.95 2.4
D
-153.0 c-212.0 18.0
C
-142.3 -209.4 14.5
C
147
-150.1 -204.0 20.8
D
47,147, 167
47,147
4
,46,53, 54.147
-
4.42
-151.5 -204.5 18.8
C
18.36, 58,147, 168,169
4.26
4.20 12.0
-140.3 -200.9 15.8
C
18,36, 147
3.36 5.9
3.21 12.4
-147.5 -222.4 12.7
D
47,167, 170
0.0 0.0
3.89
-152.2 -211.9 19.6
2-Deoxy-2-fluoro-~-mannopyranosyl fluoride
p anomer
5.01
0.0 47.4 17.8
4.41 2.7 2.8d 51.8
3.23 9.7 30.0
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
147
TABLEXLVIII (continued)
3,4,6-tn-O-acetyla anomer 5.76 4.89 5.27 5.42 4.42 4.06 9.0 10.0 2.0 2.5 48.0 0.0 2.5 0.0 0.0 0.0 4.0 48.5 27.0 p anomer 5.51 4.90 5.14 5.29 3.86 4.30 4.30 1.0 2.5 8.5 7.5 7.0 48.5 8.0 0.5 0.8 13.5 '49.0 22.4 2.0 0.5 3,4,6-Tri-0-acetyl-2-deoxy-2-fluoro-~-~-talopyranosyl fluoride 4.28-3.90 5.33 4.69 5.07 5.19 1.0 3.0 3.0 1.0 48.0 6.0 51.0 25.0 14.5
-143.4 -207.2 20.0
C
18,36
-146.4
C
18,36, 58,147, 168,I69
C
45,147
I- 277.0
13.5 -145.8 -218.4 12.8
The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Ref. 53 reported a coupling of 20 Hz. Ref. 54 reported a chemical shift of -223 p.p.m. Ref. 47 reported a coupling of 9.8 Hz; additional couplings: J (F, H-4) = 1 Hz, and J (F, H-6) = 1 Hz. 'Ref. 169 reported a coupling constant of 34 Hz. 'Ref. 147 reported a chemical shift of -220.1 p.p.m. (I
(167) N. Satyamurthy, G. T. Bida, H. C. Padgett, and J. R. Barrio, J . Carbohydr. Chem., 4 (1985) 489-512. (168) J. Adamson, A. B. Foster, L. D. Hall, and R. H. Hesse, Chem. Commun., (1969) 309-310. (169) T . Ido, C. N. Wan, J. S. Fowler, and A. P. Wolf, J . Org. Chem., 42 (1977) 23412342. (170) S. G. Withers, I. P. Street, and S. J. Rettig, Can. J . Chem., 64 (1986) 232-236.
TABLE XLIX IH- and '9F-N.m.r. Data for 3(or 4, or 6)-Deoxy-3(or4, or 6)-fluorohexopyranosyI Fluorides
3-Deoxy-3-fluoro-~-glucopyranosylfluoride 2,4,6-tri-O-acetyla anomer 5.73 5.02 4.79 5.29 4.07 4.26 4.14 2.6 9.5 9.5 9.5 12.5 52.2 22.6 1.0 0.5 51.5 13.5 1.0 4.0 14.5 p anomer 4.57 5.31 3.79 4.24 4.21 5.27 5.2 12.4 6.0 7.7 8.5 9.5 51.5 10.8 0.0 0.0 0.0 15.0 51.3 13.5 1.0 2,3,6-Tri-0-acetyl-4-deoxy~4-fluoro-~-galactopyranosy~ fluoride a anomer 2.3
9.9 24.0 2.8 R anomer
2.5 25.4
0.5
-149.8 -201.1
C
II
-138.8 -196.0 3.0
C
11
C
19
C
19
1 .o
3.7 28.0
1.0
10.5 2.5 1.0 9.6 2.5 0.8 1.3 25.6 25.2 1.0 4-Deoxy-4-fluoro-~-glucopyranosyl fluoride 2,3,6-tri-O-acetyla! anomer 5.68 4.87 5.6 4.52 4.5 2.8 10.2 8.9 9.5 52.0 23.7 3.0 0.8 14.6 48.5 p anomer 5.37 5.02 5.30 4.65 3.96 4.48 5.8 7.4 8.6 9.4 2.9 4.9 50.7 10.2 0.8 0.8 0.9 0.6 0.5 0.0 15.8 49.5 4.9 1.6 6-Deoxy-6-fluoro-~-glucopyranosyl fluoride 2,3,4-tri-O-acetyla anomer 5.75 4.94 5.50 5.17 4.03 4.51 2.7 9.9 9.4 10.0 2.2 3.5 52.4 23.8 23.9 47.0
1.0
6.7
1.3 1.0
4.12
-150.0 - 199.5 0.6
C
12
4.24 12.1 0.6 1.9
-137.0 -199.4 3.1
C
12
4.45 10.8
-150.4 -234.8 0.2
C
84
47.0
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
149
TABLEXLIX (continued)
p anomer 5.4
4.93
-
5.5
52.7
5.25 9.0
3.95
4.51
4.51
10.4 20.6
46.6
-137.0 -232.2 0.9
C
84
46.6
" The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom.
TABLEL 'H- and I9F-N.m.r. Data for Dideoxydifluorohexo-pyranosesand -pyranosides Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
Jz.3
J3,4
54.5
Js,6
55.6'
56.6'
'JFJ
JFJ
JF.~
JF,~
JFJ
JF.6
JF,~
'JF,I
JFJ
JF.3
JF,4
JF,~
JF,6
JF,~
6F1 6F2 J(F,F)
S
-118.8 - 124.3 246.0
s
171
-119.9 -141.4 241 .O
s
171
-192.5 -196.3
A
65,77
-215.0 -234.2
A
'
References
2-Deoxy-2,2-difluoro-~-urubino-hexopyranose (Y
anomer
6.0 p anomer
17.0
6.0 23.0
6.0 20.5
3,6-Dideoxy-3,6-difluoro-~~-allopyranoside methyl 4.50 3.41 8.0 1.3 29.3
4.91 53.7
3.64 10.0 29.3
3.78 4.5 25.6
methyl 2,4-di-O-benzoyl5.08 5.20 5.50 5.33 10.5 8.0 2.0 2.0 1.5 28.0 54.0 27.0
4.44 4.0 24.5
4.61 2.0 47.6 4.73 2.0 47.5
4.64 11.0
b
47.6 4.76 10.5
65
47.5 (continued)
RENE CSUK AND BRIGITTE I. GLANZER
I50
p-nitrophenyl 5.46 3.86 5.01
8.0
28.0
52.0
3.89
10.0
4.15 4.0
5.04
8.5
28.0
52.0
4.14 10.0
29.0 28.0
phenyl 5.21
4.61 4.0
4.0
48.0 4.61 2.0
65
-211.1 -234.5
65
48.0 4.12 10.0
28.0
25.0 46.0 4,6-Dideoxy-4,6-difluoro-~-galactopyranoside methyl a anomer '4.17 4.82 4.0 2.6 0.0 30.6 50.3 30.6 13.5 46.6 p anomer
-211.9 -235.5
46.0
-219.1 -229.9
172
- 196.2
71
-219.9 -230.1
65
-216.9 -231.9
27,ll
- 196.9
65
77
3
46.6 -206.2
30.5 phenyl a5.63 4.0 3.5 10.0
4.2 29.0
51.3 4.96 51.0
30.5 13.4
46.7
4.34 1.2
4.55 4.6 43.0
Methyl 4,6-dideoxy-4,6-difluoro-~-tdopyranoside a anomer
4.88 3.5
3.19
3.83
32.0
4.19
48.6
4.01
32.0 13.8
4.62
2.0 46.6
46.1 4.68 9.5 46.0 4.62 2.0 46.6
2,3-O-isopropylidene-a-
-235.1
25.0
52.0
25.0 25.0
6-Deoxy-6,6-difluorogalsetopyranose 1,2,3,4-tetra-O-acetyl-ta anomer
6.39 3.1
5.25
10.7
5.39 3.3
5.65
4.58 5.9
48.0
6.02 55.5
d
48.0
6.02
173
54.4 (continued)
I5 I
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLEL (continued)
p anomer
5.76 8.5
5.36 10.7
5.10
5.60
3.3
4.00 5.5
I ,2:3,4-di-O-isopropylidene-a-~-
5.56 4.9 1.8
4.36
4.65 7.7 1.3
4.36
3.90 6.6
5.78 55.4 -
5.78
5.5
I73
C
173, 174
54.4 5.84 57.5 54.0
10.0
C
-131.6 -133.6 298.2
a The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Ref. 65 reported chemical shifts of -217.6 and -234.6 p.p.m., respectively. Ref. 172 reported for H-1 = 4.88 p.p.m. Ref. 77 reported chemical shifts of -196.7 and -199.6 p.p.m., respectively. ' Ref. 174 reported data for the corresponding D enantiomer.
(171) J. Adamson, A. B. Foster, and J. H. Westwood, Curbohydr. Res., 18 (1971)345-347. (172) C. W.Somawardhana and E. G. Brunngraber, Carbohydr. Res., 94(1981)cl4-cl5. (173) J. A. May, Jr., and A. C. Sartorelli, J . Med. Chem., 22 (1979)971-976. (174) M.Sharma, I. Kavai, Y.L. Fu, and M. Bobek, Tetrahedron Lett., (1977)3433-3436. TABLELI IH- and I9F-N.m.r.Data for Difluorinated Anhydrohexo-pyranose and -furanose Derivatives Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
6F1
S
31.2
Jz.3
J3,4
54.5
55.6
J6.6'
6F.2
a
VF.1
JFJ
JFJ
Jp.4
JF,S
Js,~ JF,~
JF.~'
'JFJ
JF,Z
JF,~
JF.~
JF,~
JF.~
JF,~
J(F,F)
3-O-Acetyl-1,6-anhydro-2,4-dideoxy-2,4-difluoro-~-~-glucopyranose
5.57
4.38
5.13
4.23
4.78
C
17.5 17.5 45.0 1,6-Anhydro-2,4-dideoxy-2,4-difluoro-~-~-ribo-hexo-pyranos-3-ulose hydrate 5.49 4.07 4.23 4.73 4.03 3.75 S 2.2 2.I 1.2 5.9 7.2 2.2 48.0 1.0 4.0 9.6 9.6 2,5-Anhydro-l-deoxy-l,l-d~uoro-~-hexitol
References
118
45.0
arabinoa anomer
5.99 3.0
D
I75 h
176 (continued)
152
RENE CSUK AND BRIGITTE I. GLANZER TABLELI (continued)
Compound H-1 H-2
H-3
H-4
H-5
H-6
H-6'
JIS
523
53.4
54,s
55.6
53.6
J6.6'
6F1 6F2
'JPJ
JFJ
JFS
JF,4
JFJ
JF,~
Jp.6,
J(F,F)
'JFJ
JFJ
JFJ
JF,~
JF,S
JF,~
&,6*
55.1 3,4,6-tri-O-acetyI5.86 3.6 55.0 ribo5.60 5.40 4.0 54.0 12.0 12.0
-128.2
5.40
4.0
4.0
3,CAnhydro-6,6-di!luoro-~-glucofurnnose 1,2-O-benzylidene-a6.11 4.85 4.92-5.01 4.44 -82.9 3.6 4.0 -76.5 11.0 144.0 7.0 1,2-O-isopropylidene-u5.92 4.70 4.78-4.86 4.39 -82.8 3.6 4.0 -76.4 11.0 144.3 7.0 3,6-Anhydro-6,6-difluoro-l,2-O-isopropylidene-~~-idofuranose 5.92 4.76 4.69 4.95 4.24 -87.0 3.6 0.7 3.5 0.6 -68.7 0.4 3.5 5.8 3.2 150.4 1.2 0.6
S
References
a
C
176
C
177
C
125
C
125
C
125
The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. J (H-2, H-4) = 1.3 Hz. J (H-I, H-4) = 0.6 Hz; J(H-2, H-4) = 0.6 H z ; J (H-2, H-5) = 0.6 Hz; and J (H-3, H-5) = 0.6 Hz.
(175) J. PacBk, M. BraunovB, D. StropovB, and M. Cerng, Collecr. Czech. Chem. Commun., 42 (1977) 120-131. (176) K. R. Wood and P. W. Kent, J . Chem. SOC., C, (1967) 2422-2425. (177) P. W. Kent and J. E. G. Barnett, Tetrahedron, Suppl., 7 (1966) 69-74.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
I53
TABLELII 'H- and I9F-N.m.r.Data for 2,6-Dideoxy-2-fluorohexopyranosylFluorides Compound
H-1
H-2
H-3
H-4
H-5
H-6
H-6'
11.2
J2J
J3.4
54.5
J5,6
J5,v
J6,@
%,I
JFJ
JF,~
JF,~
JFJ
JF,~
JF,~
*JFJ
JF,~
JF,3
JP.4
JFJ
Jv.6
JF,~'
m1
m
S
References
0
J(F,F)
2,6-Dideoxy-2-fluoro-~-galactopyranosyl fluoride (Y
anomer
54.4 24.5 0.6 48.2 13.4 3,4-di-O-acetyl(Y anomer 3.0 53.5 0.5
9.5 23.2 48.8 13 anomer
-151.6 -212.2 19.5
D
147
-152.1 -211.9 18.3
C
147, 148b
-142.7 -210.4 15.4
C
147
C
149
C
149
4.2
3.5
2.0
11.3
3.8
6.4
52.8 14.5 4.9 51.5 13.3 2.9 3,4-Di-0-acetyl-2,6-dideoxy-2-luoro-a-~-glucopyranosyl fluoride 3.2 53.5 0.2
9.8 24.0 48.0
9.8
9.8
6.2
19.0
12.5
3,4-Di-0-acetyl-2,6-dideoxy-2-fluoro-~-~-mannopyranosyl fluoride 0.5 48.5 17.0
2.3 4.2 52.0
9.5
7.5
6.2
-148.3 -221.6 13.0
28.0
" The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Ref. 148 reported a chemical shift of -148.1 p.p.m. for F-I.
154
RENE CSUK AND BRIGITTE I. GLANZER
TABLELIII
‘Hand l9F-N.m.r.Data for Difluorinated Hex-5-enofuranoses
5,6-Dideoxy-1,2-0-isopropylidenehex-5-enofuranose 6-chloro-5,6-difluoro-3-O-methyl-a-~-xy/o(Z) isomer 5.89 4.62 3.67 4.98 5.47 -91.1 C 178 3.8 3.2 9.0 2.0 9.9 (E) isomer 5.73 4.46 3.56 4.85 5.12 -87.3 T 178 3.9 2.9 8.8 2.9 27.8 6,6-difluoro-3-O-methyl-~-~-/yxo4.91 4.98 -79.0 C I79 10.2 -74.0 b 0.3 2.3 35.3 e 0.8 25.2 6,6-difluoro-3-O-methyl-a-~-ribo4.64 4.34 -80.2 c 179 9.8 -76.8 b I .3 1.5 30.9 0.9 23.7 6,6-difluoro-3-O-methyl-a-~-xy/oC 179 -79.6 4.90 4.58 -77.5 9.5 33.5 1.7/1.1 1.6/25.0 3,5,6-Trideoxy-6,6-difluoro-1,2-O-isopropylidene-~-~-erythro-hex-5-enofuranose 5.82 4.74 1.61/2.23 4.84 4.32 -77.0 C 178 d.e. 3.7 4.6 10.7l4.5 9.1 -77.9 b 0.8 2.5 34.8 c 1.0 2.4 1,2-~-lsopropylidene-5,6-dideoxy-6,6-difluoro-cu.~-xy~o-hex-5-enofuranose 3-0-benzyl 4.9 4.67 -89.6 C I79 9.8 -87.9 b 2.0 2.0 33.4 c 2.2 23.4 3-O-methylC 179 4.90 4.58 -79.6 9.5 -77.5 b I .7 1.6 33.5 1.1
25.0 (continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
155
TABLELIII (continued)
3-O-benzyl-a-
4.91
4.67 -89.6 C 179 -87.9 9.8 d 2.0 2.0 33.4 2.2 23.4 Methyl 5,6-dideoxy-6,6-difluoro-2,3-O-isopropylidene-~-~-r~~o-hex-5-enofuranoside 4.97 4.64 4.64 4.90 4.46 -74.2 C 178 10.4 -76.1 1.2 2.8 34.0 1.2 24.0 The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Coupling to cis-oriented fluorine atom. Coupling to trans-oriented fluorine atom. J (H3, H-3') = 13.5. e Ref. 178 reported further examples for higher sugars.
(178) J. M. J. Tronchet and A. P. Bonenfant, Helu. Chirn. Acta, 63 (1980) 1644-1653. (179) J. M. J. Tronchet, A. P. Bonenfant, and F. Barbalat-Rey, Carbohydr. Res. 67 (1978) 564-573.
TABLELIV 'H- and I9F-N.rn.r.Data for Difluorinated Pentoses ~~
Compound H-1 H-2
H-3
H-4
H-5
H-5'
JI,~
52.3
J3.4
54.5
J4.5~
JS,Y
'JF,~
JFJ
JFJ
JF,~
JF,S
JF,V
'JF.1
JF3
JFJ
JF.4
JF,~
JF,Y
sF1
m
J(FJ9
3,4-D~-O-acetyl-2-deoxy.~-fluoro-~-~-arabinopyranosyl fluoride 5.86 4.31 5.50 4.16 3.85 -156.0 3.0 1.5 2.0 13.5 -210.0 53.0 0.5 2.0 2-Deoxy-2-fluoro-D-lyxopyranosy~ fluoride p anorner 3.0 53.0 4.5
3.0 22.0 45.5
3.5
2.5
S
References
C
53,54, 98
D
99
a
12.2
(continued)
RENE CSUK AND BRIGITTE I. GLANZER
I56
TABLELIV (continued) Compound H-1 H-2
H-3
H-4
H-5
JIJ
JZJ
J3.4
J4.5
54,s’
H-5’
%,I
JF,Z
JFJ
JF,~
JF.S
JFJ’
‘JFJ
JFJ
JF.~
JF,~
JF,S
JFJ~
3,4-di-O-acetyla anomer
p anomer 3.6 53.0
3.6 47.0
2.0
12.5
25.0 4.0
3,4-D~-O-acetyl-2-deoxy-2-fluoro-~-~-~bopyranosyl fluoride 5.7Sb 4.9Ib 4.0b 3.67 3.5 10.0 5.0 10.0 24.5 44.0 3,4-Di-O-acetyl-2-deoxy-2-fluoro-~-~-xylopyranosyl fluoride
5.60 3.5 53.5
2,4-Di-O-acetyl-3-deoxy-3-luoro-/3-~-xylopyranosyl fluoride
sF1
m
J(F,F)
S
a
References
-156.0 -215.0
C
54
-156.0 -215.0 19.0
C
533
-151.0 -206.0
C
98
-152.0 -212.0
C
5334
5.41 5.0 4.65 5.0 4.31 3.72 c 11 -137.7 2.7 4.7 4.7 3.0 3.5 12.8 -195.7 0.5 0.0 49.8 7.7 0.2 10.4 0.0 12.5 45.5 12.5 2.5 0.3 3,5-Dideoxy-3,5-d~uoro-l,2-O-isopropylidene-cu-~-xylofuranose 5.9 5.30 -209.8 T 2033, 4.0 -231.5 I80 1.2 11.0 49.5 29.9 1.4 11.9 46.0 Methyl 5-deoxy-5,5-difluoro-~-ribofuranoside 2,3-O-isopropylidene-PC 181 -129.0 - 129.0 Methyl 2-deoxy-2,2-difluoro-3,4-O-isopropylidene-~~-e~~~r~-pentopyranoside -126.2 C 181 - 146.1 Methyl 4-deoxy-4,4-di8uoro-2,3-O-isopropylidene-/3-~-e~~~r~-pentopyranoside C 181 -113.1 - 115.9 256.5 The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. The assignments may have to be reversed. J (H-1, H-3)= 0.5 and J (H-3, H-5’) = 0.8 Hz.
(180) A. B. Foster and R. Hems, Carbohydr. Res., 10 (1969) 168-171. (181) R. A. Sharma, I. Kavai, Y. L. Fu, and M. Bobek, Tetrahedron Lett., (1977) 34333436.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
157
TABLELV 'H- and IgF-N.m.r. Data for Difluorinated Amino Suears Compound
H-l
H-2
H-3
H-4
H-5
H-6
H-6'
J1.z
JZ.3
J3.4
54,s
554
55.6'
5 6 , ~
'JFJ
JF,Z
JFJ
JF,4
JFJ
JF.6
JF,~
*JFJ
JFJ
JFJ
Jp.4
JFJ
JF,~
JF,~
sF1
m
S
a
References
J(F,F)
Methyl 2-acetam~do-2,4,6-trideoxy-4,6-difluoro-~-~-g~actopyranos~de -225.0 P -236.7 33.8 63.0 33.8 13.5 47.3 47.3 3-0-acetyl-222.9 C -227.7 28.1 54.0 28.1 13.5 45.0 45.0 Methyl 2-acetamido-3-O-acetyl-2,4,6-tdeoxy-4,6-difluoro-~-~-glucopyranoside 3.33 -200.4 11.0 8.7 -240.8 13.5 48.4 2.8 24.8 47.3 47.3 Methyl 2-benzamido-2,4,6-tdeoxy-4,6-d~uoro-~-~-g~a~opyranoside 3-0-acetyl-223.4 -237.8 25.9 54.0 25.9 12.4 47.3 47.3 3-0-benzyl-224.0 -236.5 26.4 55.1 26.4 16.9 48.9 48.9 Methyl 2-benzamido-2,4,6-tdeoxy-4,6-difluoro-t~-glucopyranoside 3-0-acetyl5.49 -200.3 10.6 8.7 -240.8 15.8 48.4 1.1 25.9 47.3 47.3 3-0-benzyl-198.1 -240.1
134
134
134 b
134
134
134 b
134
The symbols I, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atom. Partial listing of coupling constants in A is given, too.
RENE CSUK AND BRIGITTE I. GLANZER
158
TABLELVI ‘H-and I9F-N.m.r. Data for Tri- and Tetra-fluorinated Monosaccharides
3,6-Anhydro-5-deoxy.5,6,6-trifluoro-1,2-0-isopropylidene-~-~-glucofuranose 6.00 4.78 4.94 5.07 5.35 -216.8 C 125 b 3.5 0.6 3.4 4.5 -79.3 3.5 6.3 2.0 48.0 -75.7 1.3 1.5 9.0 0.6 5.6 3,6-Anhydro-5-deox~5,6,6-triluoro-1,2-0-isopropylidene-~-~-idofuranose 5.91 4.78 5.07 4.95 5.10 -201.1 c 125 3.6 0.6 3.7 0.6 -86.6 5.6 9.4 47.4 -68.5 0.6 3.6 2.8 0.6 1.4 3,4,6-Trideoxy-3,4,6-trifluoro-c~-~-galactopyranosyI fluoride 5.84 4.21 4.94 5.27 4.57 4.80 4.73 -154.3 M 182 10.1 2.7 5.2 6.5 9.5 -221.3 d 5.4 53.0 25.0 -207.1 2.9 11.0 47.2 -232.5 26.8 51.4 28.1 14.2 47.0 47.0
“ The symbols I, m, h refer to proton-fluorine couplings with increasing number of the corresponding fluorine atoms. J (H-I, H-3) = 0.6; J (H-1, H-5) = 0.4; J (H-2, H-4) = 0.6; J (F-5, F-6) = 12.2; J (F-5, FA’)= 12.2; J (F-6, F-6’) = 140.4 Hz. J (H-1, H-3) = 0.6; J (H-2, H-4) = 0.6; J (H-2, H-5) = 0.6; J (F-5, F-6) = 12.2; J (F-6, F-6’) = 152.6 Hz. d J (F-I, F-3) = 3.7; J (F-3, F-4) = 13.7 Hz. (182) G . H.Klemm,R. J. Kaufman,and R. S . Sidhu,Tetrahedron Lett., (1982)29272930.
TABLELVII IH-and 19F-N.m.r.Data for Acyclic Monosaccharides 2,2’-O-Methylenebis(I-deoxy-l-fluoro-~-glycerol) (C, Ref. 183) H-l = H-I’ = 4.58p.p.m.; J (H-I, H-2) = 5 Hz; J (F, H-I) = J (F, H-1‘) = 45 Hz 2,2‘-O-Methylenebis(3-O-benzoyl-I-deoxy-l-fluoro-~-glycerol) (C, Ref. 183) H-1 = H-I’ = 4.63p.p.m.; J (H-I, H-2)= 4.5 Hz; J (F, H-I) = J (F, H-1’) = 47.5Hz 1,6-Dideoxy-l,6-difluorogalactitol (D,Ref. 184) = J (H-l’, F) = 50 Hz; J (H-2, F) = 18 Hz;6F = -227.6 p.p.m.
J (H-I, F)
(continued)
N.M.R.SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
159
TABLELVII (continued)
Ref. 184) 24 Hz;6F = -232.5 p.p.m.
1,6-Dideoxy-l,6-difluoro-2,3 : 4,6-di-O-isopropylidenegalactitol (s,
J (H-I, F) = J (H-l', F) = 49 Hz;J (H-2, F)
=
I ,2,4,5,6-Penta-O-acetyl-3-deoxy-3-fluoro-~-mannitol (Ref.73) in C in B [J (H,F)1 [J (H,F)1 H-l = 4.55(2.6) J(1,l') 4.63(2.6) H-I'= 4.13(2.2) 3.97(2.I ) J( 12) H-2 = 5.11 (6.8) 5.32(6.8) J( I ' 2) H-3 = 4.85(45.6) 4.87(46.0) J(2,3) H-4 = 5.66(30.I ) J(3,4) H-5 = 5.31 (0.0) 5.50 (1.0) J(43 H-6 = 4.38(0.0) 4.48(0.0) J(5,6) H-6' = 4.16(0.0) 4.17(0.0) J(5,6') J(6,6')
in C
in B
12.5 2.5 4.3 9.3 1.6 7.1 2.6 5.7 12.5
12.4 2.6 4.8 9.3 1.7 7.2 2.7 5.4 12.6
3,4-O-Benzylidene-l,6-dideoxy-l,6-difluoro-2,5-O-methylene-~-mannitol (C, Ref. 183) H-l = H-I'= H-6= H-6'= 4.71 p.p.m.; J (H-I, F) = J (H-l', F) = 47.5Hz. 1,6-D~deoxy-1,6-difluoro-2,5-O-methylene-~-mannito~ (A,Ref. 183) H-l= H-I'= H-6= H-6'= 4.66p.p.m.; J (H-I, F) = J (H-l', F) = 47.5Hz. 3-Deoxy-l-fluoro-3-iodo-l,2 :5,6-di-O-isopropylidene-a-~-xy/o-4-hexulose (B, Ref. 185) H-l= 6.13;H-2= 4.84;H-3= 4.64p.p.m.;J (H-I, H-2)= I : O Hz;J (H-2, H-3)= 10 Hz;J (F, H-I)= 66 Hz;J (F, H-2)= 15 HZ
1,2-Dideoxy-l, I-difluoro-3,4 : 5,6-di-O-isopropylidene-~-arabino-hex-I-enitol (C,Ref. 179)" F) = 1.5 Hz;J(H-2, F') = 23.8Hz;H-3= 4.62p.p.m.; H-2= 4.39p.p.m.;J(H-2, J (H-3, F) = 1.5 Hz;J (H-3, F') = 0.9Hz;J (H-3, H-4)= 9.3Hz;6F-1 = -79.0p.p.m.; 6F-2 = -76.6 p.p.m.; J (F, F')= 32.8Hz " Partial "C-n.m.r. data also given: C-1 = 157.7 p.p.m., J (C, F) = J (C, F') = 293.7 Hz; C-2 = 78.9 p.p.m., J ( C , F) = 24.0 H z ; J ( C , F') = 16.2 Hz; C-3 = 73.2 p . p . m . . J ( C ,F) = 8.7 H z ; J ( C , F') = 0.0 Hz. (183) W. J. Lloyd and R. Harrison,Carbohydr. Res., 26 (1973)91-98. (184) E. M.Acton,M.Keyanpour-Rad,J. E. Christensen,H.H.Tong, R.P.Kwok,and L.Goodman,Carbohydr. Res., 22 (1972)477-486. (185)A.A.Akhrem,N.B. Khripach,and I. A. Mikhailopulo,Carbohydr. Res., 50 (1976) ~6-~8.
RENE CSUK AND BRIGITTE I. GLANZER
I60
TABLELVIII W-N.m.r. Data for Hexopyranosyl Fluorides Compound
c-1
c-2
c-3
c-4
c-5
C-6
JFJ
JFJ
JFJ
JF,~
JF,S
JF,~
2,3,4,6-Tetra-0-scetyl-~-altropyranosyl fluoride a anorner 104.3 67.7 66.2 64.0 66.4 226.7 38.8 0.9 0.5 2.4 p anorner 105.0 67.1 67.7 64.5 74.7 1.1 227.4 22.9 2,3,4,6-Tetra-0-acetyl-~-galactopyranosyl fluoride a anorner 66.9 104.3 67.3 67.3 68.8 228.3 24.1 3.7 p anorner 107.2 69.2 70.1 66.6 71.3 1.2 217.3 24.9 10.5 4.7 D-Glucopyranosyl fluoride a anorner 69.4 108.2 71.9 73.3 75.0 222.2 24.8 2.9 p anorner 110.0 "76.0 "73.6 69.9 "76.9 211.3 22.1 2.2 4.3 2,3,4,6-tetra-O-acetyla anomer 67.I 103.7 69.9 69.2 69.7 228.9 24.3 4.4 p anorner 106.3 71.3 71.9 67.6 72.1 219.4 29.3 8.8 4.46 3,4,6-tri-O-acetyl-2-O-methyl(Y anorner 103.9 78.4 71.0 67.4 69.5 229.9 23.4 4.4 p anorner 108.4 80.3 72.5 67.7 71.3 217.4 24.9 10.6 4.8 2,4,6-tri-O-acetyl-3-O-rnethyia anomer 103.9 72.0 77.7 68.4 70.0 227.4 24.7 4.6 p anorner 106.1 71.0 79.6 67.9 72.1 218.3 27.8 5.9 3.8
s
References
62.0
C
28
63.2 2.1
C
28
61.1
C
28
61.4
C
28
61.O
D
28
61.4
D
24,28
61.0
C
28
61.9
C
24,28
61.3
C
28
61.5
C
28 e
61.4
C
28
62.2
C
28 (continued)
161
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES TABLELVIII (continued)
Compound c-1 c-2 JF,~
JF,~
c-3
c-4
C-5
C-6
JF.3
JFA
JFS
JF,~
D-Mannopyranosyl fluoride 2,3,4,6-tetra-O-acetylQ anomer 104.7 67.6 68.1 65.0 70.8 223.1 39.7 1.8 3.1 p anomer 104.1 67.8 68.4 66.4 72.7 223.6 25.0 5.9 4.4 3,4,6-tri-O-acetyl-2-O-methyl-a104.6 75.9 70.1 64.8 70.0 35.2 I .o 224. I 2.9 2,4,6-tri-O-acetyl-3-O-methyl-a66.4 70.9 105.0 65.9 76. I 221.2 39.6 2.9 2,3,4,6-Tetra-0-acety1-a-~-talopyranosyl fluoride 104.5 64.6 65.4 65.1 65.8 224.7 36.6 2.9 1.8
S
References
61.7
C
28
62.7
C
28
61.4
C
28
62.0
C
28
61.8
C
28
The assignments may have to be reversed. Ref. 28 reported a coupling of 2.1 Hz. J (F, OMe) =
Hz.
TABLELIX W-N.m.r. Data for 2(or J)-Deoxy3(or 3)-fluorohexo-pyranoses and -pyranosides
Compound c-1 (2.2 JFJ
JF.Z
c-3
c-4
C-5
C-6
JF.3
JF,~
JF,S
JF.~
1,3,4,6-Tetra-~-acetyl-2-deoxy-2-fluoro-a-~-gdactopyranose 89.0 84.1 68.2 67.8 68.6 61.0 22.3 191.1 18.9 7.5 Methyl 2-deoxy-2-fluoro-~-gdactopyranoside p anomer 101.2 91.6 71.3 69.3 75.4 60.9 23.2 179.4 17.1 8.5 3,4,6-tri-O-acetyl-p101.6 88.0 71 .O 67.7 70.6 61.1 22.0 186.8 20.8 8.5 2-Deoxy-2-fluoro-~-glucopyranose Q anomer 90.9 91.5 72.4 70.4 72.5 61.6 21.4 185.9 17.5 8.0 1.3
S
References
C
49,50
D
26
C
26
D
24,57 (continued)
RENE CSUK AND BRIGITTE I. GLANZER
I62
TABLELIX (continued) Compound
c-1
c-2
c-3
c-4
c-5
C-6
JF,~
JF,~
JFJ
JF,~
JFb
JF,~
77.3 1.2
61.8
D
2437
70.0
61.8
C
4930
73.6
61.8
D
24,63, 64
77.3
62.0
D
24,63, 64
73.1
61.7
C
49,50
C
64
A
65
A
65
C
186
C
I86
D
26,186
C
26,186
C
69
p anomer 94.7 94.1 75.3 70.6 23.0 183.1 17.3 8.2 I ,3,4,6-tetra-O-acetyl-a88.8 86.6 71.0 67.9 21.8 194.2 19.4 7.5 2-Deoxy-2-fluoro-D-mannopyranose a anomer 92.5 91.6 70.7 68.1 29.6 172.2 17.5 I .4 p anomer 93.6 92.6 73.1 67.9 15.8 180.0 17.6 1.5 1,3,4,6-tetra-O-acetyl-P90.4 86.5 71.3 65.0 15.4 191.2 17.1
s
References
Benzyl3,4,6-tn-O-benzyl-2-deoxy-2.luoro-fi-~-mannopyranoside 97.0 86.9 80.7 15.9 188.0 18.3 Methyl 3-deoxy-3-fluoro-fi-o-allopyranoside 102.0 67.4 93.7 70.3 74.5 62.0 2.9 16.I 176.0 16.1 6-O-pivaloyl-p101.8 67.4 93.4 70.2 72.0 63.7 3.0 17.6 177.9 16.1 2.9 1,2,4,6-Tetra-O-acetyl-3-deoxy-3.luoro-~-gdactopyranose a anomer 89.7 85.4 8.6 192.9 p anomer 91.5 68.9 88.7 66.7 71.5 61.1 11.0 19.5 195.3 17.1 3.0 2.4 Methyl 3-deoxy-3-fluoro-~-gdactopyranoside p anomer 103.2 69.5 93.2 67.0 74.0 60.7 11.0 19.5 183.1 17.1 7.3 3.6 2,4,6-tri-O-acetyl-p101.3 69.7 88.8 66.9 69.8 61.2 11.0 19.5 192.9 17.1 6.1 2,4-di-O-benzoyl-6-0-(bromoacetyl)a anomer 97.7 70.0 85.9 68.8 66.3 63.8 6.1 8.6 18.3 192.9 17.1
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
163
TABLELIX (continued)
Compound c-1 c-2
References
c-3
c-4
C-5
C-6
JFS
JF,~
JF,~
JF.6
67.8 17.6
70.2 6.2
63.4 3.1
C
69
93.5 71.2 96.2 69.1 10.9 16.8 178.6 17.6 p anomer 96.4 73.8 97.8 69.1 12.4 17.2 180.5 17.6 3-Deoxy-3-fluoro-~-mannopyranose a anomer 94.2 68.9 92.3 65.4 7.0 15.0 183.0 18.0 p anomer 93.0 69.5 93.7 65.1 11.0 17.0 183.0 19.0
72.0 7.3
61.4 1.5
D
24
65.8 8.2
61.6 1.9
D
24
72.0 6.0
60.7
D
187
74.8 7.0
60.7
D
187
JF.I
JF.1
S
p anomer 101.7 9.5
70.6 18.9
88.9 195.8
3-Deoxy-3-fluoro-~-glucopyranose a anomer
(186) P. KovBt and C. P. J. Glaudemans, Curbohydr. Res., 123 (1983) 326-331. (187) J. R. Rasmussen, S. R. Tafuri, and S. T. Smale, Curbohydr. Res., I16 (1983) 21-29.
TABLELX W-N.m.r. Data for 4(or 6)-Deoxy4(or 6)-fluorohexo-pyranosesand -pyranosides
Compound c-1 c-2
c-3
c-4
JF,~
JFJ
JF.~
JFJ
c-5
4-Deoxy-4-fluoro-~-gdactopyranose a anomer 93.6 69.6 “69.2 91.7 “70.5 2.2 17.6 177.0 17.6 p anomer 97.4 73.1 72.8 90.8 74.8 1.1 18.0 177.7 17.3 Methyl 4-deoxy-4-fluoro-~-galactopyranoside a anomer 100.9 69.6 69.7 91.8 71.9 2.6 18.0 177.4 17.6 p anomer 90.9 75.0 104.9 72.0 73.0 178.2 17.6 17.9
C-6
S
61.3 5.5
D
24
61.1 5.5
D
24
61.5 5.5
D
65,188
61.3 5.1
D
26,188
References
(continued)
RENk CSUK AND BRIGITTE I. GLANZER
164
TABLELX (continued) Compound c-1
c-2
c-3
c-4
c-5
C-6
JFJ
JFJ
JFJ
Jp.4
JF3
JF,~
2,3,6-tn-O-acetyla anomer 97.3 67.9
S
References
“66.7 17.7
87.1 185.3
“68.3 17.7
61.9 5.9
C
50
“70.8 18.3
85.9 185.6
“71.8 17.1
61.4 4.9
C
26
78.9 86.0 73.5 17.9 17.7 182.9 2,3-di-O-benzyl-6-0-trityl-p104.4 78.9 79.0 86.2 72. I 17.1 17.1 184.3 4-Deoxy.4-fluoro-D-glucopyranose a anomer 93.2 72.2 a72.3 90.5 “70.1 1.4 8.3 17.6 179.9 23.9 p anomer 97.1 74.9 “75.0 90.3 “72.3 1.4 8.8 18.0 180.0 24.5 4-Deoxy.4-fluoro-~-mannopyranose a anomer 69.9 94.0 71.4 68.7 88.5 9.0 18.0 176.0 24.0 p anomer 73.5 93.8 71.7 71.3 88.3 11.0 18.0 176.0 24.0 Methyl 4-deoxy-4-fluoro-a-~-tdopyranoside 102.0 69.9 66.7 90.0 70.0 17.6 16.1 179.0 Methyl 6-deoxy-6-fluoro-~-gdactopyranoside p anomer 104.0 70.6 72.6 68.4 73.4 20.8 7.3 2,3,4-tri-O-acetyl-p101.8 68.6 70.1 66.9 71.3 23.2 6.1 6-Deoxy-6-fluoro-~-glucopyranose a anomer 93.5 72.6 73.9 69.8 71.5 0.7 6.6 17.2 p anomer 97.3 75.3 76.8 69.7 75.6 6.9 18.7
60.9 5.3
D
26,76 1886
61.6 2.4
C
26
61.2
D
24
61.4
D
24
60.5
D
187
60.4
D
187
60.5 7.4
A
65
83.1 164.8
D
26
80.7 171.5
C
26
83.7 167.2
D
24
83.5 167.6
D
24
p anomer
101.7
68.6
2,3-di-O-benzyl-p104.6 79.0
(continued)
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
165
TABLELX (continued) Compound c-1 c-2 JF,l
JFJ
S
References
84.8 168.4
A
27,77
82.3 170.9
A
65,77
82.2 170.6
A
65
82.5 170.6
A
65
82.5 170.6
A
65
83.5 170.6
A
65
82.8 170.6
A
65
83.4 170.6
A
65
c-3
c-4
c -5
C-6
JF.3
JF,~
JF,S
JF,~
Methyl 6-deoxy-6-fluoro-~-glucopyranoside a anomer 102.0 73.7 75.5 71.0 73.0 6. I 17.1 /3 anorner 103.8 73.5 76.7 69.0 74.7 7.3 18.3 p-Nitrophenyl6-deoxy-6-fluoro-/3-~-glucopyranoside 100.5 73.6 76.9 68.9 75.5 7.4 17.6 Phenyl6-deoxy-6-fluoro-~-glucopyranoside a anomer 98.5 72.5 74.2 69.4 72.0 4.4 13.2 /3 anomer 101.0 73.7 77.0 69.1 75.2 7.4 17.6 Methyl 6-deoxy-6-fluoro-or-D-mannopyranoside 102.2 72.6 71.5 67.3 72.5 7.4 19.1 2,3-di-O-rnethyl98.9 76.4 81.6 65.4 72.3 7.4 17.6 2,3-O-isopropylidene79.9 76.5 68.6 70.1 99. I 7.3 17.6 * The assignments may have to be reversed.
Ref. 188 reported some data for the a anomer.
(188) J. E. Nam Shin, A. Maradufu, J. Marion, and A. S. Perlin, Carbohydr. Res., 84
(1980) 328-335.
TABLELXI UC-N.m.r. Data for Hexofuranogl Fluorides and Deoxyfluorohexofuranoses Compound c-1 c-2 JFJ
JFS
c-3
C-4
c-5
C-6
JFJ
JF.4
JFJ
JF,~
76.7 1.2
67.6 0.7
62.4
D-Glucofuranosyl Ouoride 2,3,5,6-tetra-O-acetyla anomer 106.9 78.2 73.1 234.2 19.6
S
C
References
28 (continued)
RENE CSUK AND BRIGITTE I. GLANZER
166
TABLELXI (continued)
Compound
References
c-1
c-2
c-3
c-4
c-5
C-6
JF,I
JF,Z
JFS
JF.~
JF,S
JF,6
80.4 2.5
68.2
62.5
C
28
76.8 1.2
67.8 0.9
62.6
C
28
80.1 2.4
68.5
62.8
C
28
81.1
68.7 1.2
62.5
C
28
81.9 2.6
69.3
63.1
C
28
69.8 0.9
78.0 2.1
67.7
62.4
C
28
68.3
77.9 2.4
67.1 1.2
62.2
C
28
C
28
C
89,89a
C
89,89a
C
2530
D
91
D
91
p anomer 111.5 79.0 71.7 228.5 35.4 3,5,6-tri-0-acetyl-2-O-methyla anomer 107.7 86.2 74.0 233.8 18.9 p anomer 112.2 87.0 71.6 226.5 31.4 2,5,6-tri-0-acetyl-3-O-methyla anomer 106.7 77.1 77.7 231.6 19.5 p anomer 112.3 77.8 81.7 227.3 34.5 0.7 D-Mannofuranosyl fluoride
1.5
S
(1
3,5,6-tri-O-acetyl-2-O-methyl-
a anomer 112.6 76.0 225.2 36.0 p anomer 106.5 71.6 236.8 20.1
2,5,6-tri-O-acetyl-3-O-methyl-~-
1.5
62.1 78.1 68.4b 106.7 80.7 66.3b 234.4 20.5 2,3 : 5,6-di-O-isopropylidenea anomer 66.0 72.6 82.6b 113.7 84.7 78Sb 221.5 41.8 p anomer 81.1b 66.5 73.6 107.5 81.2 77.6b 235.6 22.0 1,2 :5,6-Di-O-isopropylidene-3-deoxy-3-fluoro-~-~-glucofuranose 104.8 82.3 93.5 80.4 71.7 66.9 33.8 183.0 19. I 7.4 5-Deoxy-5-fluoro-D-glucofuranose a anomer 97.5 76.4 75.7 76.4 92.0 62.0 28.4 167.7 19.1 p anomer 103.1 81.0 75.3 79.2 92.0 62.3 28.4 167.7 20.5
(continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
167
TABLELXI (continued) Compound c-1 c-2 JFJ
JF,Z
c-3
c-4
c-5
C-6
JFJ
JF,~
JF,S
JF,6
78.8 30.9
91.5 167.6
62.9 19.1
A
91
80.2 17.7
93.6 172.9
61.8 20.0
D
91
77.3 17.7
94.5 170.6
61.8 20.0
D
91
80.7 19.1
94.6 170.6
62.0 22.0
A
91
1,2-O-isopropylidene-a106.1 86.3 74.7
5-Deoxy-5-fluoro-~-idofuranose a anomer 102.6 81.1 75.2 5.8 p anomer 96.7 76.5 75.2 5.8 1,2-O-isopropylidene-p105.7 86.4 75.2 8.8 J (F, OMe)
=
S
0.9 Hz. * The assignments may have to be reversed
TABLELXII W-N.m.r. Data for Fluorinated Pentopyranose Derivatives
2,3,4-Tri-O-acetyl-P~-arabinopyranosyl fluoride 104.6 67.5 68.1 66.4 62.4 C 28 227.1 26.4 2.8 2,3,4-Tri-0-acetyl-~-xylopyranosylfluoride a anomer 103.8 70.3 68.8 68.0 60.1 C 28 228.5 23.4 4.4 p anomer 105.3 67.0 67.1 66.8 60.6 C 28 222.8 36.0 2.8 0.6 3.4 l,3,4-Tr~-O-acetyl-2-deoxy-2-fluoro-&o-arbinopyranose 89.5 84.3 67.8 69.0 62.5 C 49,50 22.1 191.1 18.7 6.8 1,3,4-Tri-~-acetyl-2-deoxy-2-fluoro-cr-~-l~opyranose C 49,50 89.6 79.6 68.6 67.7 61.8 19.1 192.7 17.6 2.9 1,3,4-Tri-0-acetyl-2-deoxy-2-fluoro-~-ribopyranose a anomer 88.9 84.0 67.2 “65.3 “61.0 C 49,50 20.0 198.1 16.7 (continued)
References
RENE CSUK AND BRIGITTE I. GLANZER
I68
TABLELXII (continued) Compound C-1 C.2 JFZ
JFJ
C-3
C-4
C-5
JFJ
JFA
JFJ
S
References
p anomer 90.8 84.7 66.0 66.1 62.8 C 101 30.5 189.2 18.3 1,3,4-Tri-0-acetyl-2-deoxy-2-fluoro-cu-~-xy~opyrmose 88.8 86.6 70.2 68.3 60.6 C 49,50 20.6 194.4 19.1 7.4 Methyl 4-deoxy-4-fluoro-~-arahinopyranoside a anomer 60.1 D 65 99.4 67.9 67.5 90.3 19.1 173.5 19.1 p anorner 104.6 71.7 72.2 89.4 64.0 C 65 22.0 177.9 20.6 a
The assignments may have to be reversed.
TABLELXIII W-N.m.r. Data for Fluorinated Pentofuranose Derivatives Compound C-1 C-2 JFJ
JFZ
C-3
C-4
C-5
JFS
JF.4
JF.S
o-Arabinofuranosyl fluoride 2,3,5-tri-O-benzoyl-a-~112.7 80.9 76.7 84.4 63.5 225.8 40.3 2,3 ,S-tri-O-benzyl-a-~113.5 224.6 2,3,5-tri-O-benzyl-P-~108.3 228.8 o-Lyxofuranosyl fluoride 5-0-benzoyl-2,3-benzoxonium-a114.2 97.1 95.5 84.3 66.7 229.4 47.1 2,3,5-tri-O-benzoyla anomer 112.3 75.7 70.8 78.3 62.9 224.7 37.4 1.8 1.8
S
References
C
28
C
105,106 a
C
105
F
107
C
28 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES TABLELXIII (continued) Compound C-1 C-2 JF.I
J F ~
C-3
C-4
C-5
JFJ
JFR
JF.S
S
References
p anomer 107.1 72.7 68.5 79.0 63.1 C 28 236.1 20.5 1.2 2.6 D-Ribofurnnosyl fluoride 2,3-acetoxonium-5-0-acetyl-P115.5 98.1 97.0 88.5 69.6 F 107 230.9 47.1 2.9 2,3,5-tri-O-benzoyla anomer 107.4 71.9 69.6 82.9 63.6 C 28 234.4 20.5 p anomer 112.4 75.0 71.4 81.3 64.3 C 28 225.5 35.9 1.5 2.9 0.5 2.3,s-tri-0-benzyla anomer 108.5 C 106 232.5 p anomer 112.4 C 106 224.0 2,3,S-Tn-O-benzoyl-cu-~-xylofurnnosyl fluoride 112.3 80.2 73.8 81.6 63.2 C 28 228.0 36.8 l-O-Acetyl-2-deoxy-2-fluoro-S-O-( methoxymethyl)-a-~ribofurnnose 94.2 88.1 69.9 84.7 66.7 C 49,50 16.0 200.3 17.0 3.0 3-Deoxy-3-fluoro-1,2-O-isopropylidene-cu-~-~~o-pentodinldo-1,4-furanose 105.9 94.9 197.0 C I I4 182.6 6.9 " Ref.
105 reported data for the
D
enantiomer.
169
RENI? CSUK AND BRIGITTE I. GLANZER
I70
TABLELXIV W-N.m.r. Data for Fluorinated Sugar Acids and Lactones Compound C-1 C-2 JF.l
JF,Z
C-3
C-4
C-5
C-6
JFS
JF,4
JF5
JF.6
References
S
5-Deoxy-5-fluoro-a-~-glucofuranurono-6,3-lactone 1,2-O-isopropylidene107.6 82.7 81.7 76.6 86.2 168.0 C 5.9 14.7 206.9 23.8 5-Deoxy-5-fluoro-&~-idofuranurono-6,3-lactone 1,2-O-benzylidene105.1 82.3 84.5 81.0 87.5 169.0 C 28.2 179.8 20.0 1,2-O-isopropylidene106.5 82.2 85.1 80.0 87.3 169.1 C 28.0 185.3 20.6
91
125 91
TABLELXV W-N.m.r. Data for Fluorinated Amino Sugars and Their N-Containing, Synthetic Precursors
Compound C-1 C-2 JF.1
JF.Z
C-3
C-4
C-5
C-6
JF,3
JF.4
JF.5
JF,6
S
References
3-Azido-4,6-0-benzylidene-3-deoxy-~-~-allopyranosyl fluoride 108.5 76.7 61.4 77.1 64.1 67.8 C 214.9 22.9 9.8 4.6 Benzyl 2-fluoro-cu-D-dtropyranoside 3-azido-4,6-O-benzylidene-2,3-dideoxy96.4 88.0 57.7 75.9 59.3 69.2 C 34.3 174.9 28.9 3-benzamido-2,3,6-trideoxy96.6 87.2 50.3 70.4 65.4 17.4 C 31.0 178.6 26.9 Methyl 2,3,6-trideoxy-2-fluoro-cr-~-altropyranoside 3-amino64.5 17.6 C 98.5 89.1 50.6 67.8 32.0 176.0 24.0
127
I27 132
133
3-(trifluoroacetarnido)-
97.7 86.1 49.9 68.7 64.4 30.2 178.0 28.1 3-benzamido-4-O-benzoyl-6-bromo98.5 86.6 47.0 67.7 67.0 30.7 179.8 28.3
17.4
C
133
31.9
C
133 (conrinued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
I7 I
TABLELXV (continued)
3-benzamido-4-0-benzoyl98.4 86.9 46.9 70.1 62.7 17.5 C 133 18.1 8.3 30.8 179.2 Benzyl 2,3,6-trideoxy-2-fluoro-fi-~-galactopyranoside 3-benzamido100.3 89.6 54.0 72.0 71.8 16.1 B 132 22.8 187.4 17.8 8.1 4-0-benzoyl-3-(trifluoroacetamido)99.8 88.2 53.1 72.2 71.1 16.4 C 127 22.3 189.1 18.7 7.1 Methyl 2,3,6-trideoxy-2-fluoro-/3-~-galactopyranoside 3-amino101.6 92.7 55.6 72.2 71.9 16.3 C I33 18.1 8.3 23.0 180.4 3-(trifluoroacetamido)55.5 71.2 72.1 16.4 C 133 102.6 89.1 22.4 184.0 16.1 7.8 3-benzamido-4-0-benzoyl102.3 88.9 52.7 73.2 70.9 16.4 C I33 21.5 187.5 17.5 7.8 Methyl 3-benzamido-4-O-benzoyl-2,3,6-tndeox~2-fluoro-c~-~-u~u~i~ohex-5-enopyranoside 100.1 86.9 48.5 66.7 149.8 99.5 C 133 180.1 27.3 31.5 Methyl 6~azido-3,6-dideoxy-3-fluoro-fi-~-allopyranoside 102.0 70.4 93.5 68.2 73.8 52.0 A 65 18.0 3.0 0.0 3.4 17.0 177.7 Benzyl 4,6-0-benzylidene-2,3-dideoxy-3-fluoro-c~-~-glucopyranoside 2-azido80.1 62.6 68.8 C 127 98.0 62.3 88.7 8.8 17.4 189.1 17.2 7.6 2-benzamidoP 132 99.0 54.5 89.5 80.9 63.4 69.2 9.0 17.1 191.0 16.5 7.5 Methyl 4-azido-4,6-dideoxy.6-fluoro-c~-~-glucopyranoside 100.5 72.8 73.5 61.7 69.2 82.7 A 65 5.9 17.6 172.0 3-Acetamido-2,3,5,6-tetradeoxy-5-fluoro-fi-~~-~i~o-hexofuranose 99.8 40.2 49.6 85.3 91.7 16.3 C 140 20.8 167.2 22.0 Methyl 3-aceta~do-2,3,5,6-tetradeoxy-5-fluoro-~~-~i~o-hexofuranoside a anomer 103.6 39.3 48.4 86.1 90.3 16.8 C 140 43.9 180.7 22.0 (continued)
RENB
I72
CSUK AND BRIGITTE I. GLANZER TABLELXV (continued)
Compound C-1 C-2 JF.1
JF.2
p anomer 105.6 39.3
C-3
C-4
C-5
C-6
JF,3
JF.4
JFJ
JF,6
50.7
88.3 20.7
90.3 180.7
16.8 22.0
S
References
C
140
TABLELXVI W-N.m.r. Data for Branched or Deoxy Fluorinated Monosaccharides
Compound C-1 C-2 JF.1
JF3
C-3
C-4
C-5
C-6
JF,3
JF.4
JF5
JF.6
~
S
References
~~
Methyl 4,6-0-benzylidene-2-deoxy-3-C-[ (ethoxycarbony1)-(fluoromethyl)]-a-~-ribbo-hexopyranoside (I?) isomer 98.2 36.2 71.5 77.2 58.7 69.2 C 189 3.3 19.5 (S)isomer 98.4 33.8 71.0 77.4 58.9 69.1 C 189 1.4 22.0 1.1 b Methyl [benzyl 2-(benzyloxycarbonyl)amino-2,3,4-trideoxy-5-fluoro-aD-erythro-hex-3-enopyranosid]uronate 94.6 46.9 132.1 122.6 97.3 166.0 B 126 8.4 27.5 224.3 37.4 1-0-Acetyl-2,3,5,6-tetra-O-benzoyl-4-fluoro-~~-g~actofuranose 98.8 79.7 75.5 70.1 62.2 C I59 0 21.1 35.7 2.2 1-0-Acetyl-2,3,5,6-tetra~O-benzoyl-4-fluoro-~-~-glucofuranose 102.0 79.0 77.2 120.7 70.6 62.5 A 159 41.2 232.1 26.4
1-0-Acetyl-2,3,5-tri-O-benzoyl-4-fluoro-a-~-lyxofuranose
99.4 74.9 74.6 118.2 62.4 C 159 2.5 0.0 42.0 232.7 30.2 l-O-Acetyl-2,3,5-tri-O-benzoyl-4-fluoro-~-~-nbofuranose 98.3 73.1 70.1 114.4 62.8 - C 159 0.0 0.0 18.0 237.5 44.4 Methyl 2,4-di-0-benzoyl-6-0-(bromoacetyl)-3-deoxy-3-fluoro-a-~galactopyranosyl chloride 91.1 69.3 85.5 67.9 69.7 62.9 C 69 9.1 18.9 193.1 17.1 4.7 4.0 2,3,4-Tri-0-acelyl-6-deoxy-a-~-glucopymnosyl fluoride 103.8 70.8 69.5 72.7 67.9 17.1 C 28 227.7 24.7 4.6 (continued)
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES TABLELXVI (continued)
Compound C-1 C-2 JF.2
JF,l
C-3
C-4
C-5
C-6
JF,3
JF.4
JFJ
JF.6
S
References
2,3,4-Tri-O-acetyl-6-deox~cu-~-mannopyranosyl fluoride 104.7 67.8 68.1 69.8 68.7 17.1 C 221.3 41.3 2.1 3.1
28
* CO: 167.7 p.p.m.; J (C-F) = 24.4 Hz; CHF (of fluoromethylene): 88.2 p.p.m.; J (C-F) = 194.1 Hz; partial IH-n.m.r. data also given. CO: 167.5 p.p.m.; J (C-F) = 23.8 Hz; CHF (of fluoromethylene): 86.2 p.p.m.; J (C-F) = 186.8 Hz; partial IH-n.rn.r. data also given.
(189) S. Brandange, 0. Dahlman, and L. Morch, J . Am. Chem. Soc., 103 (1981) 4452-4458.
TABLELXVII W-N.m.r. Data for Fluorinated Ketopyranoses and Derivatives
Compound C-1 C-2 JFJ
JFJ
C-3
C-4
C-5
C-6
JFJ
JF.4
JF.5
JF.6
S
References
l-Deoxy-l-fluoro-2,3 :4,5-di-O-isopropylidene-~-fructopyranose 82.2 101.2 69.9 70.2 70.9 61.1 C 160 174.0 21.5 2.0 1.o 4-Deoxy-4-fluoro-~~-fructopyranose 63.6 98.6 66.2 91.6 67.5 62.7 D 161 1.6 9.7 18.3 180.1 16.6 7.0 4-Deoxy-4-fluoro-a-~-sorbopyranose 64.2 99.1 69.8 96.8 68.8 61.8 C 161,190 10.0 17.0 178.0 17.0 10.0
~-~eox~4-fluoro-1,2-O-~sopropyl~dene-~-~-tagatopyr~ose
72.3
105.4
67.4 26.0
90.7 178.0
64.3 17.0
61.8
C
190
59.9 26.0
C
190
5-Deoxy-5-fluoro-cu-~-sorbopyranose 64.3
98.4
71.0 7.0
73.2 17.0
" An additional coupling, J (F,Me)
90.2 178.0 = 2.9 Hz, is
observed (6 Me
=
24.7).
(190) G. V. Rao, L. Que, Jr., L. D. Hall, and T. P. Fondy, Carbohydr. Res., 40 (1975) 311-321.
173
RENE CSUK AND BRIGITTE I. GLANZER
I74
TABLELXVIII W-N.m.r. Data for Mono- and Di-fluorinated Ketofuranose Derivatives Compound C-1 C-2 JYJ
JF,Z
C-3
C-4
C-5
C-6
JFJ
JF,~
JFJ
JF,~
S
References
C
I63
C
I63
A
I64
A
164
1,3,4,6-Tetra-O-acety~-~-fructofuranosyl fluoride
a anomer 61.2 117.5 78.2 83.5 76.7 62.7 28.8 226.8 46.0 1.5 0.2 0.5 p anomer 61.7 113.9 75.0 80.2 74.7 63.6 43.7 232.8 20.9 2.8 0.4 Methyl 1-deoxy-1-fluoro-D-fructofuranoside a anomer 78.6 108.0 81.3 79.4 86.3 62.8 170.9 20.8 p anomer 81.6 102.7 79.1 76.7 83.4 63.7 174.6 19.5 3,4,6-tri-O-benzoyI-p-
C 164 173.3 19.3 6-Deoxy-6-fluoro-2,3-O-isopropylidene-l-O-p-tolyls~onyl-~-~-fructofuranose 68.2 113.9 83.6 74.9 86.7 81.8 C 164 4.9 20.8 170.9 1,6-Dideoxy-1,6-difluoro-2,3-O-isopropylidene-~-~-fructofuranose 81.2 113.3 86.8 75.2 86.7 82.2 C 164 172.0 23.2 a 4.9 20.8 177.0 b Methyl 1,6-dideoxy-1,6-difluoro-~-fructofuranoside a anomer 79.3 107.4 81.9 78.0 82.9 83.5 A 164 172.1 20.8 b 7.3 19.5 170.9 p anomer 81.4' 102.9 79.0 75.3 81.3' 83.6 A 164 174.5 19.5 0 7.3 18.3 172.1 b Coupling to fluorine at C-1, Coupling to fluorine at C-6. The assignments may have to be reversed.
N.M.R. SPECTROSCOPY O F FLUORINATED MONOSACCHARIDES
TABLELXIX W-N.m.r. Data for Difluorinated Monosaccharides, Including Anhydro and Unsaturated Derivatives Compound
C-1
C-2
C-3
C-4
C-5
C-6
JF.1
JF,2
JF.3
JF,4
JF.5
JF.6
JF.1
JF.2
JFJ
JF.4
JFJ
JF,6
S
References a
b
3,6-Dideoxy-3,6-difluoro-~-~-allopyranoside methyl 102.1 70.7 93.6 ‘66.3 ‘73.0 83.1 A 65,77 4.3 17.2 177.0 d25.0 7.9 ‘4.3 20.0 170.9 phenyl 65 99.0 70.0 93.6 73.1 65.8 82.5 A 4.4 17.0 177.9 17.6 8.0 2.9 17.6 172.0 Methyl 4,6-dideoxy-4,6-difluoro-~-galactopyranoside (Y anomer 77 102.5 ‘69.9 ‘70.5 92.8 ‘71.5 84.9 A 178.2 6.1 6.1 167.2 p anomer 77 105.1 ‘71.8 ‘72.5 89.8 ‘72.6 82.6 A 180.7 6.1 6.7 167.9 Methyl 4,6-dideoxy-4,6-difluoro-cu-~-talopyranoside 102.0 69.4 65.3 ‘81.9 67.5 %9.6 C 27,77 16.1 ’158.0 22.1 87.4 7.4 17.6 172.0 3,6-Anhydro-6,6-diBuoro-a-~-glucofuranose I ,2-O-benzylidene125 105.1 84.9 84.1 82.1 74.2 128.7 C 6.0 31.0 265.0 26.0 260.0 1,2-O-isopropylidene125 106.1 83.2 83.4 79.6 72.9 127.3 C 1.8 2.0 6.2 30.0 264.0 1.6 25.0 248.0 3,6.Anhydro-6,6-difluoro-1,2-~-isopropylidene-~-~-idofuranose I25 106.1 85.5 86.7 82.9 74.9 130.2 C 2.0 3.0 37.0 259.0 22.0 259.0 5,6-Dideoxy-6,6-difluoro-1,2-O-isopropylidene-u-~-xylo-hex-5-enofuranose 3-0-benzyl73.7 75.1 157.2 C 179 26.2 292.5 8.8 0.0 15.9 289.0 (continued)
175
RENE CSUK AND BRIGITTE I. GLANZER
176
TABLELXIX (continued)
3-O-methyl-
73.4 74.9 157.1 C 179 27.0 292.4 9.2 0.0 10.8 288.5 5,6-Dideoxy-6,6-diffuoro-l,2-O-isopropylidene-3-O-methyl-~-~-/y~o-hex-5enofuranose 73.2 78.6 157.6 C 179 22.5 290.3 7.5 0.0 16.2 290.3 5,6-Dideoxy-6,6-diffuoro-l,2-O-isopropylidene-3-O-methyl-~-~-ribo-hex-5enofuranose 71.8 78.0 158.4 C 179 25.3 293.9 8.7 0.0 16.5 290.0 6-Chloro-5,6-dideoxy-5,6-difluoro-l,2-O-isopropylidene-3-O-methyl-a-D-~/ohex-5-enofuranose ( E ) isomer 104.6 85.1 81.8 73.9 101.9 146.3 C 178 12.4 306.7 (Z) isomer 104.7 85.2 81.90 76.7 101.4 147.0 C 178 8.3 23.8 301.2 Methyl 5,6-dideoxy.6,6-difluoro-2,3-O-isopropylidene-a-~-ri~o-hex-5-enofuranoside 109.6 85.6 79.7 85.4 80.4 156.8 C 178 h 7.4 11.9 20.5 291.5 0.0 17.4 3,5,6-Trideoxy-6,6-diffuoro-l,2-O-isopropylidene-~-~-e~r~ro-hex-5enofuranose 105.2 80.5 39.8 70.8 79.3 157.3 C 178 h 7.8 23.7 288.8 i 0.0 16.5 292.4 a The couplings refer to the “lower”-numbered fluorine atom. The couplings refer to the “higher”-numbered fluorine atom. The assignments may have to be reversed. Ref. 65 reported a coupling of 17.6 Hz. Ref. 65 reported a coupling of 2.9 Hz.f Ref. 77 reported a coupling of 180 Hz (solvent A). * Ref. 77 reported a coupling of 5.5 Hz (solvent A). * Coupling to cis-oriented fluorine atom. Coupling to trans-oriented fluorine atom.
N.M.R. SPECTROSCOPY OF FLUORINATED MONOSACCHARIDES
I77
TABLELXX W-N.m.r. Data for Tri- and Tetra-fluorinated Monosaccharides Compound c-1
c-2
c-3
c-4
c-5
C-6
JFJ
JFJ
JF3
JF.~
JF5
JF,6
JFJ
JFJ
JFJ
JF.~
JFJ
JF,6
JFJ
JFJ
JFJ
JF,~
JF5
JF.6
JFJ
JFJ
JFJ
JF.~
JF,S
JF,6
References
S
3,6-Anhydro-5-deoxy-5,6,6-trifluoro-l,2-O-isopropylidene-cu-~-glucofuranose 106.0 83.8 83.0 77.6 88.1 126.5 C 125 14.0 204.0 266.0 b 4.0 33.0 250.0 b 24.0 22.0 3,6-Anhydro-5-deoxy-5,6,6-trifluoro-l,2-O-isopropylidene-~-~-idofuranose 105.4 86.0 81.7 80.9 89.7 126.7 C 125 L7 3.0 30.0 188.0 258.0 b 42.0 258.0 b 22.0 22.0 3,4,6-Trideoxy-3,4,6-trifluoro-cu-~-galactopyranosyl fluoride 108.95 67.95 89.41 88.09 71.20 81.78 M 182 226.8 53.0 22.7 11.0 22.7 188.7 3.7 e 2.0 18.4 181.7 21.0 b 6.6 21.0 169.3 ' Coupling to fluorine at C-5. Coupling to fluorine at (2-6. Coupling to fluorine at C-I. Coupling to fluorine at C-3. Coupling to fluorine at C-4.
TABLELXXI W-N.m.r. Data for Fluorinated Neuraminic Acid Derivatives Compound
C-1
C-2
C-3
C-4
C-5
C-6
C-7
C-8
C-9
JF.1
JF,Z
JF,3
JF,~
JF,S
JF,6
JF.~
JF,~
JF,~
S
References
Methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,S-dideo~2-nonulosylfluoride)onate ff-D-glyCer0-aD-gUhCt0165.9 106.9 35.9 68.7 49.0 73.4 67.5 69.9 62.3 C 191 30.0 223.6 25.0 8.6 ff-D-glyCer0-P-D - g U h C t O 165.0 108.0 35.5 68.5 48.6 73.2 29.7 231.0 28.3 N-Acetyl-9-deoxy-9-fluoroneuraminic acid 175.5 96.4 39.1 67.8 53.2 71.5 a
67.4
70.4
62.5
C
191 n
68.5 7.2
69.9 17.8
86.4 164.9
D
Partial 'H-n.m.r. data reported, too. 6F = -235.4 p.p.m.
(191) M. N. Sharma and R. Eby, Carbohydr. Res., 127 (1984) 201-210. (192) M. Sharma and W. Korytnyk, J . Carbohydr. Chem., 1 (1982-1983) 311-315.
192 b