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Regio- and stereo-controlled synthesis of core oligosaccharides of glycopeptides
Gubohydrate Research. 64 (1978) C3-C9 0 Elsevier Scientific Publishing Company, Amsterdam
c3 - Printed in The Netherlands
Preliminary communication Regio- and stereo-controJ!ledsynthesis of core oligosaccharides of glycopegtides
TOMOYA OGAWA*, KIYOAKI KATANO*: -%ndMASANAO MATSUI 7ke Institute
of Physical and Chemical Research,
Wake-shi, Srn-tama, 351 (Japan)
(Received April 19th, 1978; accepted for publication,
May Sth, 1978)
As a result of recent studies on the biochemistry of oligosaccharides present at cell surfaces, many of them have been found to have branchedchain structures’ and to be linked to asparagine; and these may be classified into two types. For example, ollgosaccharide 1 (which was isolated from immnnoglobulin glycopeptide’) and o_hgosaccharide 2 (which was isolated from calf thyroglobnlin3 ) may respectively be classified as an N-acetyllactosamine type, or type A, and an oligo-D-mannosidic type, or type B, of oligosacchaCT-SA.-(2--6l-#l-Gal-(1--4)-p-GlcNAc-(1-2)_Cr-Man 1
6 p-Man-(l-4)-p-GlcNAc-(1-4)-P-GlcNAc_1-Asf 3
t 1 CX-S.A.-(2~6+3-Gol-(l-4+G-Gl~NA~-~l~2~-a-Man
S.A.
=
sialic
1
acid
a-Mm-Cl-2ka-Man 1
+
6 U-Mot-~-l
i\ 1 a+mn-c~-2~-a-r40n
B-
Mon-(l-4)-p-GlcNAc-(l-4)-pGlcNAC-l-ASP 1
t 1
2
*To whom enquiries should be addressed. **Research feYow from the Research Laboratories of Meiji Seii ku-ku, Yokohama, 222, Japan.
Kaisha, Ltd., Morooka*ho,
Koho-
PELIhiINARY
c4
COMMUNICATION
ride4. Not only their biological functions’ but also their unique, branched-chain structures have stimulated efforts directed toward their chemical synthesis6 . As part of a project on the chemical transformation of carbohydrates through trialkylstannyiation, we report here a synthesis of core pentasaccharides, both of type A (22) and type B (17). The reaction of tributyitin a&oxide’ (4) with 2,3,4,6-tetra_O-acetyi-a-D -mannopyranosyi bromide (3) was reported’ to afford a high yield of orthoester 5. Moreover, a regioseiective enhancement of the nucieophilicity of the hydroxyi groups of methyl Or-Dmannopyranoside (6) by tributyistannyiation and subsequent treatment with such eiectrophilic reagents as an acyl halide9 or an alkyl halideI was reported to give a high yieici of methyl 3,6diGsubstituted a-D -mannopyranoside (7). Consequently, if a giycosyi halide such as 9 is used as an eiectrophik reagent, instead of a simple alkyl halide, for the reaction with 6, a re$ocontrolled introduction of two D-mannosyi residues might be expected to occur at O-3 and O-6, via orthoesters. C,f+OAc ROSnB%
(4) _
AKI-I-?_-
5
C,HzOH HO (2)
RX OMe
OMe 6
7
In fact, the reaction of 20acetyi-3,4,6-triU-benzyia-D -mannopyranosyi chloride [RF 0.76 in 1:4 toiuene-ethyl acetate; ‘H-n_m.r. data (in CD(&): 6 2.12 (s, 3 H, COCH3), 5.44 (t, 1 H, J 2 Hz, H-2), and 6.03 (d, 1 H, J 2 Hz, H-l), which was prepared by the reaction of orthoester 8 with cblorotrimethylsiiane’l] with partially stannyiated 6, prepared in the usual way g11o through reaction with 1.5 molar proportions of bis(tributyltin) oxide, afforded a 34% yield*?* of 10, a molecule containing an orthoester form at O-3 and O-6 of methyl a-D-marmopyranoside, <[aID t40.0’ (c 0.52, CH&)****;RF* O-48 (4: 1 CHQJ -acetone); ‘H-n_m.r. data (in CDC13): 6 1.76 (s, 3 H, C-CHs) and 1.83 (s, 3 H, C-CHs) 3 and a 2.2% yield of a molecule containing an orthoester form at 04 and O-6 bf methyl a-D-mannopyranoside, {[&ID +38.5* (c 0.46, CHCls); RF 033 (4:l CHCis-acetone); ‘H-n_m.r. data (in CD&): 6 I.73 (s, 3 H, C-CH=,) and 1.82 (s, 3 H, CCHB)) _ ***Yields are not optimized. ****All compounds for which [a]D is recorded gave an acceptable, elemental analysis. ;Thin-laYa chromatography was performed on precoated plates of Silica Gel 60 F,, _
PFUXIMINARY
COMMUNICA~ON
CS
Treatment of 10 with sodium hydride and cY-bromotoluene in NJV-dimethylformamideI afforded a 773% yield of per-U-benzylated 10 (11) {[a]D +45S” (c 0.44, CHCls); RF 0.86 (2: 1 toluene-ethyl acetate); ‘H-n.m.r. data (CDCls): 6 1.74 (s, 3 H, C-CHs) and 1.86 (s, 3 H, C-CHs) ). R earrangement of 11 into the protected trimannoside 12 {[a]* i-41.7’ (c 0.59, CHCls); RF 0.36 (4: 1 toluene-ethyl acetate); ‘H-nm.r. data (CD&): 6 2.06 (s, 3 H, COCHB) and 2.13 (s;3 H, COCH,)} was achieved in 273% yield by heating at 120” in the presence of HgBr2 under N 2 _Deacetylation of 12 with sodium methoxide in methanol-tetrahydrofuran afforded an 83.8% yield of diol 13, the key intermediate for further transformation {[&ID G3.8’ (c 0.47, cHcla);R~ 0.37 (2:l toluene-ethyl acetate)}. The (r stereochemistry was assigned to the two newly introduced D-mannosidic linkages in 13 by measuring the r3C-n.m.r. data (Da 0 ) for methyl 3,6-d&O-o-D-mannopyranosyla-D-mannopyranoside (14) {[o]D +96.7’ (c 0.45, MeOH);RF 02 (1:3:1 CHCLMeOH-cont. N&OH); ‘H-n_m.r_:data (CD,OD): 6 336 (s, 3 H, OCHs), 4.60 (d, 1 H,J 1.5 Hz), 4.83 (d, 1 H, J 1.5 Hz), and 5.06 (d, 1 H, J 2.0 Hz) for three anomeric protons 1, obtained by hydrogenolysis of 13 in ethanol i&the-presence Three ano- _ _.- -- of lO%EdX. merit carbon atoms were observed, at 6 100.1 (‘Ja 170.9 Hz, C-la), 101.8 (rJcD 171.9 Hz, C-l), and 1032 (‘Jcrr 1699 Hz, C-lb), in accordance with the ‘JcH value for the CYD-glycosyl stereochemis&y’3 (see Fig. 1).
t
9
6-
Cl
10
10R
=
11 R =
H
12R’
=
8n.R’
Bn
13R’
=
B&R’=
14R’=
9’~
=
AC
AMe
H H
Reaction of 13 with 9 in the presence of silver triflate and tetramethyIurea14 in dichloromethane under N2 afforded a 78.8% yield of the protected penta-D-mannoside 15 { [o]D +34.7’ (c 0.5 1, CHCls); RF 0.67 (4: 1 toluene-ethyl acetate) ). Deacetylation of 15 afforded a 78.1% yield of 16 {[o]D i45.9’ (c 0.7, CHCls);R, 0.26 (4:l toluene-ethyl acetate) 3, which was hydrogenolyzed in aq. ethanol in the presence of 10% Pd-C to afford methyl 3,6di-O-(2_Osr-D -mannopyranosyla-D -mannopyranosyl)a-D-mannopyranoside (17) {[aiJD +89.6’ (c 0.51, MeOH);R, 0.18 (3:l MeOH-cont. NT&OH)). The 13Cn.m.r. spectrum of 17 in D20 showed five anomeric carbon atoms: 6 98.7 (‘Jc.D 170.0 Hz,
PRELIMINARY
C6
100
90
I
I
I
80
70
60
COMMUNICATION
p.p.m. Fig. 1.25.05~MHz, Fourier-transform, “C-n.m_r. spectrum of compound 14 in D,O. (Top: protoncoupled spectrum by gated-decoupling technique; bottom: proton noisedecoupled spectrum. Chemical shifts from Me,Si).
C-la), 170.0
101.6 (‘Jm 170.0 Hz, C-lb), 101.7 (‘J CH 170.0 HZ, C-1), and 103.0 (l.+.~ Hz, C-lc and C-ld), in accordance with the assigned stereochemistry (see Fig. 2).
The key intermediate 13 could also be transformed into the core saccharide 22 (a type A oligosaccharide). Thus, the reaction of 3,4,6-t&U-acetyl-2deoxy-2-phthalimido@-D-ghrcopyranosyl chloride’* (18) with 13 in the pres ence of silver triflate and s-collidine in nitromethane afforded a 43.7% yield of protected pentasaccharide 19 {[o]D f12.0’ (c 0.59, CHCIJ);RF 0.4 (2: 1 toluene-ethyl acetate) 3. Treatment of 19 with boiling ethanolic hydrazine hydrate” under reflux-in an atmosphere of argon afforded 20. Acetylation of 20 with acetic anhydride in methanol gave a 45.8% yield of the IV-acetylated pentasaccharide 21 {[a] D +21.3O (c 0.47, CH&); RF 0.43 (4: 1) CHCls-MeOH)) . Hydrogenolysis of 21 in the presence of 10% Pd-C in aq. ethanol afforded methyl 3,6di-O[2-0(2-acetamido-2deoxyPD-glucopyranosyl)-or-D-mumopyranosyl] -a-D-mannopyranoside (22) {[a] D i-44.2” (c 0.5 1, MeOH); RF 0.27 (4: 1 MeOH-conc. NH.J OH)) The assigned stereochemistry was confirmed by the following ‘3C-n.m.r. data (DaO): 6 97.5 (‘fa 169.9 Hz, C-la), 100.4 (‘J CD 160.0 Hz, C-1c and C-ld), 100.4 (‘Ja 168.0 Hz, C-lb), and 101.8 (‘JCH 172.9 Hz, C-l) (see Fig. 3). In conclusion, regiocontrolled activation of the hydroxyl groups of methyl a-Drnannopyranoside through tributylstannylation was successfully applied to the synthesis of the core pentasaccharides of glycoproteins.
PRELIMINARY COMMUNICATION
CP
OMe .5n.RP=
AC
16 R’=
Bn.R’=
H
17 R’ =
R+ =
75
170.0
R’=
H
19 R’ =
AC,RZZ
2OR’=
d
=
=
~htl’aloyl,d
H,R3
=
21 R’ =
H,R’,
=
22R’
R3 =
H$,=Ac,H
=
Ac.,,_R’
=
Bn
Bn =
Bn
Hz
liO.0 Hz 170.0
I
I
I
II
I
I
Hz
~~ I
, 100
F&. 2.25.05MHz,
.
I .
I
I
I
90
I
60
I
70
60
Fourier-transform,
p43.m.
17 in D,O. vap: protoncoupIed spectrum by gatexklecoupling technique; bottom: proton noise-decoupled spectrum. Chemicat
shifts t-om Me, Si).
“C-IMII.~. spectrwn of compound
PRELIMINARY
C8
COMMUNICATION
168.0 Hz
I
I
100
90
I
80
I
I
I
70
60
50
o.p.m. Fig. 3. X.05-MHz, Fourier-transform, ‘“C-n.m.r. spectrum of compound 22 in D,O. (Top: protoncoupled spectrum by gateddecoupling technique; bottom: proton noise-decoupled spectrum. Chemical shifts from hfe,Si). ACKNOWLEDGMENTS
We thank Dr. H. Ho11-~naand his staff for the elemental analyses, and Dr. J. Uzawa and Mrs. T. Chijimatsu for recording and measuring the n.m.r. spectra. REFERENCES 1 2 3 4 5 6 7 8 9
10
R. Komfeld and S. Komfeld, Annu. Rev. Biochem., 45 (1976) 217-237. J. Baenziger, S. Komfeld, and S. Kochwa,J. Biol. Chem.. 249 (1974) 1897-1903; J. Baenziger and S. Komfeld, ibid. 249 (1974) 7260-7269. S. Ito, K. Yamasbita, R. G. Spiro, and A. Kobata, J_ Biochem. (Tokyoj, 81 (1977) 1621-1631. J. Montreuil, Pure Appl. Chem.. 42 (1975) 431-477. K. W. Talmadge and M. M. Burger, ikfZ?Int. Rev. Sci. Biochem. Ser. One, 5 (1975) 43-94. C. Au&, S. David, and A. Veyrikes, J. Chem. Sot. Chem. Cornmu& (1977) 449-450. A. G. Davies,Synrhetis, (1969) 56-64. T. Ogawa and M. kfatsui, Clzrbohydr. Res., 51 (1976) C13-Cl8. T. Omwa and M. Matsui, chrbohydr. Res., 56 (1977) Cl-C6. T. Ogawa and M. Matsui, Cbrhohydr. Rer, 62 (1978) Cl-C4.
. 5
PRELIMINARY
COMMUNICATION
c9
. 11 12 13
14 15
.
M. S. Newman and D. R. Olson,J. Org. Chem. 38 (1973) 4203-4204. _ J. S. Brimacombe,Merho& Gzrbohydr. Chem. 6 (1972) 376-378. K. Bock, I. Lundt, and C. Federsen, Tetrahedron Lett.. (l973) 1037-1040; K. Bock and C. Peder sen, J. them. Sot Perkin Trans. 2, (1974) 293-297;Acta &em. Scam?. Ser. B. 29 (1975) 258264. S. Hanessian and J. Banoub, Gwbohydr. Res.. 53 (1977) C13-C16. S. Akiya and T. Osawa, C7zem. Pharm. BuO.. 8 (1960) 583-587; R. U. Lemieux, T. Takeda, and B. Y. Chung,ACSSymp. Ser.. 39 (1976) 90-115.
c3 - Printed in The Netherlands
Preliminary communication Regio- and stereo-controJ!ledsynthesis of core oligosaccharides of glycopegtides
TOMOYA OGAWA*, KIYOAKI KATANO*: -%ndMASANAO MATSUI 7ke Institute
of Physical and Chemical Research,
Wake-shi, Srn-tama, 351 (Japan)
(Received April 19th, 1978; accepted for publication,
May Sth, 1978)
As a result of recent studies on the biochemistry of oligosaccharides present at cell surfaces, many of them have been found to have branchedchain structures’ and to be linked to asparagine; and these may be classified into two types. For example, ollgosaccharide 1 (which was isolated from immnnoglobulin glycopeptide’) and o_hgosaccharide 2 (which was isolated from calf thyroglobnlin3 ) may respectively be classified as an N-acetyllactosamine type, or type A, and an oligo-D-mannosidic type, or type B, of oligosacchaCT-SA.-(2--6l-#l-Gal-(1--4)-p-GlcNAc-(1-2)_Cr-Man 1
6 p-Man-(l-4)-p-GlcNAc-(1-4)-P-GlcNAc_1-Asf 3
t 1 CX-S.A.-(2~6+3-Gol-(l-4+G-Gl~NA~-~l~2~-a-Man
S.A.
=
sialic
1
acid
a-Mm-Cl-2ka-Man 1
+
6 U-Mot-~-l
i\ 1 a+mn-c~-2~-a-r40n
B-
Mon-(l-4)-p-GlcNAc-(l-4)-pGlcNAC-l-ASP 1
t 1
2
*To whom enquiries should be addressed. **Research feYow from the Research Laboratories of Meiji Seii ku-ku, Yokohama, 222, Japan.
Kaisha, Ltd., Morooka*ho,
Koho-
PELIhiINARY
c4
COMMUNICATION
ride4. Not only their biological functions’ but also their unique, branched-chain structures have stimulated efforts directed toward their chemical synthesis6 . As part of a project on the chemical transformation of carbohydrates through trialkylstannyiation, we report here a synthesis of core pentasaccharides, both of type A (22) and type B (17). The reaction of tributyitin a&oxide’ (4) with 2,3,4,6-tetra_O-acetyi-a-D -mannopyranosyi bromide (3) was reported’ to afford a high yield of orthoester 5. Moreover, a regioseiective enhancement of the nucieophilicity of the hydroxyi groups of methyl Or-Dmannopyranoside (6) by tributyistannyiation and subsequent treatment with such eiectrophilic reagents as an acyl halide9 or an alkyl halideI was reported to give a high yieici of methyl 3,6diGsubstituted a-D -mannopyranoside (7). Consequently, if a giycosyi halide such as 9 is used as an eiectrophik reagent, instead of a simple alkyl halide, for the reaction with 6, a re$ocontrolled introduction of two D-mannosyi residues might be expected to occur at O-3 and O-6, via orthoesters. C,f+OAc ROSnB%
(4) _
AKI-I-?_-
5
C,HzOH HO (2)
RX OMe
OMe 6
7
In fact, the reaction of 20acetyi-3,4,6-triU-benzyia-D -mannopyranosyi chloride [RF 0.76 in 1:4 toiuene-ethyl acetate; ‘H-n_m.r. data (in CD(&): 6 2.12 (s, 3 H, COCH3), 5.44 (t, 1 H, J 2 Hz, H-2), and 6.03 (d, 1 H, J 2 Hz, H-l), which was prepared by the reaction of orthoester 8 with cblorotrimethylsiiane’l] with partially stannyiated 6, prepared in the usual way g11o through reaction with 1.5 molar proportions of bis(tributyltin) oxide, afforded a 34% yield*?* of 10, a molecule containing an orthoester form at O-3 and O-6 of methyl a-D-marmopyranoside, <[aID t40.0’ (c 0.52, CH&)****;RF* O-48 (4: 1 CHQJ -acetone); ‘H-n_m.r. data (in CDC13): 6 1.76 (s, 3 H, C-CHs) and 1.83 (s, 3 H, C-CHs) 3 and a 2.2% yield of a molecule containing an orthoester form at 04 and O-6 bf methyl a-D-mannopyranoside, {[&ID +38.5* (c 0.46, CHCls); RF 033 (4:l CHCis-acetone); ‘H-n_m.r. data (in CD&): 6 I.73 (s, 3 H, C-CH=,) and 1.82 (s, 3 H, CCHB)) _ ***Yields are not optimized. ****All compounds for which [a]D is recorded gave an acceptable, elemental analysis. ;Thin-laYa chromatography was performed on precoated plates of Silica Gel 60 F,, _
PFUXIMINARY
COMMUNICA~ON
CS
Treatment of 10 with sodium hydride and cY-bromotoluene in NJV-dimethylformamideI afforded a 773% yield of per-U-benzylated 10 (11) {[a]D +45S” (c 0.44, CHCls); RF 0.86 (2: 1 toluene-ethyl acetate); ‘H-n.m.r. data (CDCls): 6 1.74 (s, 3 H, C-CHs) and 1.86 (s, 3 H, C-CHs) ). R earrangement of 11 into the protected trimannoside 12 {[a]* i-41.7’ (c 0.59, CHCls); RF 0.36 (4: 1 toluene-ethyl acetate); ‘H-nm.r. data (CD&): 6 2.06 (s, 3 H, COCHB) and 2.13 (s;3 H, COCH,)} was achieved in 273% yield by heating at 120” in the presence of HgBr2 under N 2 _Deacetylation of 12 with sodium methoxide in methanol-tetrahydrofuran afforded an 83.8% yield of diol 13, the key intermediate for further transformation {[&ID G3.8’ (c 0.47, cHcla);R~ 0.37 (2:l toluene-ethyl acetate)}. The (r stereochemistry was assigned to the two newly introduced D-mannosidic linkages in 13 by measuring the r3C-n.m.r. data (Da 0 ) for methyl 3,6-d&O-o-D-mannopyranosyla-D-mannopyranoside (14) {[o]D +96.7’ (c 0.45, MeOH);RF 02 (1:3:1 CHCLMeOH-cont. N&OH); ‘H-n_m.r_:data (CD,OD): 6 336 (s, 3 H, OCHs), 4.60 (d, 1 H,J 1.5 Hz), 4.83 (d, 1 H, J 1.5 Hz), and 5.06 (d, 1 H, J 2.0 Hz) for three anomeric protons 1, obtained by hydrogenolysis of 13 in ethanol i&the-presence Three ano- _ _.- -- of lO%EdX. merit carbon atoms were observed, at 6 100.1 (‘Ja 170.9 Hz, C-la), 101.8 (rJcD 171.9 Hz, C-l), and 1032 (‘Jcrr 1699 Hz, C-lb), in accordance with the ‘JcH value for the CYD-glycosyl stereochemis&y’3 (see Fig. 1).
t
9
6-
Cl
10
10R
=
11 R =
H
12R’
=
8n.R’
Bn
13R’
=
B&R’=
14R’=
9’~
=
AC
AMe
H H
Reaction of 13 with 9 in the presence of silver triflate and tetramethyIurea14 in dichloromethane under N2 afforded a 78.8% yield of the protected penta-D-mannoside 15 { [o]D +34.7’ (c 0.5 1, CHCls); RF 0.67 (4: 1 toluene-ethyl acetate) ). Deacetylation of 15 afforded a 78.1% yield of 16 {[o]D i45.9’ (c 0.7, CHCls);R, 0.26 (4:l toluene-ethyl acetate) 3, which was hydrogenolyzed in aq. ethanol in the presence of 10% Pd-C to afford methyl 3,6di-O-(2_Osr-D -mannopyranosyla-D -mannopyranosyl)a-D-mannopyranoside (17) {[aiJD +89.6’ (c 0.51, MeOH);R, 0.18 (3:l MeOH-cont. NT&OH)). The 13Cn.m.r. spectrum of 17 in D20 showed five anomeric carbon atoms: 6 98.7 (‘Jc.D 170.0 Hz,
PRELIMINARY
C6
100
90
I
I
I
80
70
60
COMMUNICATION
p.p.m. Fig. 1.25.05~MHz, Fourier-transform, “C-n.m_r. spectrum of compound 14 in D,O. (Top: protoncoupled spectrum by gated-decoupling technique; bottom: proton noisedecoupled spectrum. Chemical shifts from Me,Si).
C-la), 170.0
101.6 (‘Jm 170.0 Hz, C-lb), 101.7 (‘J CH 170.0 HZ, C-1), and 103.0 (l.+.~ Hz, C-lc and C-ld), in accordance with the assigned stereochemistry (see Fig. 2).
The key intermediate 13 could also be transformed into the core saccharide 22 (a type A oligosaccharide). Thus, the reaction of 3,4,6-t&U-acetyl-2deoxy-2-phthalimido@-D-ghrcopyranosyl chloride’* (18) with 13 in the pres ence of silver triflate and s-collidine in nitromethane afforded a 43.7% yield of protected pentasaccharide 19 {[o]D f12.0’ (c 0.59, CHCIJ);RF 0.4 (2: 1 toluene-ethyl acetate) 3. Treatment of 19 with boiling ethanolic hydrazine hydrate” under reflux-in an atmosphere of argon afforded 20. Acetylation of 20 with acetic anhydride in methanol gave a 45.8% yield of the IV-acetylated pentasaccharide 21 {[a] D +21.3O (c 0.47, CH&); RF 0.43 (4: 1) CHCls-MeOH)) . Hydrogenolysis of 21 in the presence of 10% Pd-C in aq. ethanol afforded methyl 3,6di-O[2-0(2-acetamido-2deoxyPD-glucopyranosyl)-or-D-mumopyranosyl] -a-D-mannopyranoside (22) {[a] D i-44.2” (c 0.5 1, MeOH); RF 0.27 (4: 1 MeOH-conc. NH.J OH)) The assigned stereochemistry was confirmed by the following ‘3C-n.m.r. data (DaO): 6 97.5 (‘fa 169.9 Hz, C-la), 100.4 (‘J CD 160.0 Hz, C-1c and C-ld), 100.4 (‘Ja 168.0 Hz, C-lb), and 101.8 (‘JCH 172.9 Hz, C-l) (see Fig. 3). In conclusion, regiocontrolled activation of the hydroxyl groups of methyl a-Drnannopyranoside through tributylstannylation was successfully applied to the synthesis of the core pentasaccharides of glycoproteins.
PRELIMINARY COMMUNICATION
CP
OMe .5n.RP=
AC
16 R’=
Bn.R’=
H
17 R’ =
R+ =
75
170.0
R’=
H
19 R’ =
AC,RZZ
2OR’=
d
=
=
~htl’aloyl,d
H,R3
=
21 R’ =
H,R’,
=
22R’
R3 =
H$,=Ac,H
=
Ac.,,_R’
=
Bn
Bn =
Bn
Hz
liO.0 Hz 170.0
I
I
I
II
I
I
Hz
~~ I
, 100
F&. 2.25.05MHz,
.
I .
I
I
I
90
I
60
I
70
60
Fourier-transform,
p43.m.
17 in D,O. vap: protoncoupIed spectrum by gatexklecoupling technique; bottom: proton noise-decoupled spectrum. Chemicat
shifts t-om Me, Si).
“C-IMII.~. spectrwn of compound
PRELIMINARY
C8
COMMUNICATION
168.0 Hz
I
I
100
90
I
80
I
I
I
70
60
50
o.p.m. Fig. 3. X.05-MHz, Fourier-transform, ‘“C-n.m.r. spectrum of compound 22 in D,O. (Top: protoncoupled spectrum by gateddecoupling technique; bottom: proton noise-decoupled spectrum. Chemical shifts from hfe,Si). ACKNOWLEDGMENTS
We thank Dr. H. Ho11-~naand his staff for the elemental analyses, and Dr. J. Uzawa and Mrs. T. Chijimatsu for recording and measuring the n.m.r. spectra. REFERENCES 1 2 3 4 5 6 7 8 9
10
R. Komfeld and S. Komfeld, Annu. Rev. Biochem., 45 (1976) 217-237. J. Baenziger, S. Komfeld, and S. Kochwa,J. Biol. Chem.. 249 (1974) 1897-1903; J. Baenziger and S. Komfeld, ibid. 249 (1974) 7260-7269. S. Ito, K. Yamasbita, R. G. Spiro, and A. Kobata, J_ Biochem. (Tokyoj, 81 (1977) 1621-1631. J. Montreuil, Pure Appl. Chem.. 42 (1975) 431-477. K. W. Talmadge and M. M. Burger, ikfZ?Int. Rev. Sci. Biochem. Ser. One, 5 (1975) 43-94. C. Au&, S. David, and A. Veyrikes, J. Chem. Sot. Chem. Cornmu& (1977) 449-450. A. G. Davies,Synrhetis, (1969) 56-64. T. Ogawa and M. kfatsui, Clzrbohydr. Res., 51 (1976) C13-Cl8. T. Omwa and M. Matsui, chrbohydr. Res., 56 (1977) Cl-C6. T. Ogawa and M. Matsui, Cbrhohydr. Rer, 62 (1978) Cl-C4.
. 5
PRELIMINARY
COMMUNICATION
c9
. 11 12 13
14 15
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