- Email: [email protected]
Azabicyclo[3.3.0]octanes and 6-hydroxytetrahydroquinolines from intramolecular reactions of alkenyl(amino)carbene complexes with alkynes.
~
TetYaMdron Leiters. Vol. 36, No. 48, pp. 87~3·8756, 199~ Elsevier Science lid Prinled in Greal Brilain
Pergamon
0040-4039195 $9.50+0.00
0040-4039(95)01923-5
Azabicyclo[3.3.0]octanes and 6·Hydroxytetrahydroquinolines from Intramolecular Reactions of Alkenyl(amino)carbene Complexes with Alkynes. Annette Rahm and William D. WullT* Department of Chemislly The University of Chicago Chicago. Illinois 60637
Abstract: The intramolecular reactions of alkenyl substituted amino carbcne complcxes with alkyne functional groups tethered through the nitrogen substituent of the carbene carbon are examined. These cyclizations were expected 10 occur with incorporation of CO 10 bicyclic nitrogcn hctrocyclic compounds containing a phenol function. This was found 10 be the case with complexes with three-carbon spacers between the nitrogen and alkyne where 6-hydroxytetrahydroquinolines were produced. In contrasl, complexes with two-carbon spacers gave )·azabicyclo[J,3.0)octanes that resulted from cyclization without CO insertion.
Much is known about the reactions of Fischer carbene complexes with alkynes) but the intramolecular reactions of alkenyl(arnino) carbene complexes with alkynes have not been examined. Despite the very large number of products that could potentially result from this reaction,} the possiblity that this reaction could provide a new route to 5-hydroxyindoles was sufficiently attractive to warrant an investigation given the biological importance of this class of molecules. 2 Evidence to suppon the expectation that the intramolecular reaction of complex 1 will produce 5-hydroxyindolines comes from the recent finding that alkenyl(amino) carbene complexes will react with terminal alkynes in an intermolecular fashion to give 4-aminophenol products of the type 4 in moderate to good yields.3 The simplest amine tethered alkyne that could be used is l-amino-3-butyne4 and this unit was introduced by the standard aminolysis reaction. The styryl carbene complex 6 was prepared in 63 % yield from the methoxyl complex S5 by treatment with one equivalent of the amine at ·78 0C and then warming to 25 OC for 15 Seheme I
H~3 A2~: A'
H
2
benzene
H»~'M' R'
4
8753
Me
39·64%
8754
minutes. The tenninal alkyne function that was obtained in the initial product of this reaction was silylated to give complex 6 since it is known in intramolecular reactions of alkoxy carbene complexes with alkynes that the yields are significantly lower with a tenninal alkyne function. 6 The alkenyl amino carbene complex 6 was obtained as a 1.3 : 1 mixture of geometrical isomers due to hindered rotation about the nitrogen-carbene carbon bond and which were assigned on the basis of their NMR spectral data? as the E and Z isomers, respectively.8 These isomers were readily separated by chromatography on silica gel with a 1: 1: 10 mixture of ether:CH2CI2:hexane and their thennolysis was studied independently. The geometry of the carbene complex 6 did not have an effect on the intramolecular reaction with the alkyne unit as both isomers gave the same product in the same yield, however, the product observed was not a 5-hydroxyindoline, but rather the 1• azabicyclo[3.3.0]octane chromium carbonyl complex 7. The same outcome was observed for the carbene complex 9 which was obtained by aminolysis of complex 89 and thennolyzed as a 1:1 mixture of isomers as a 0.25 M solution in benzene to give the tricyclic imine complex 10. While the complex 11 could be prepared, this material was unstable and decomposition during purification was readily evident. Several compounds were produced in the decomposition which have not yet been identified but do not appear to involve carbon-carbon bond fonnation between the carbene carbon and the alkyne function and do not include cinnamaldehyde or 1• amino-3-butyne which may be expected from the decomposition of secondary amino carbene complexes. to The fonnation of the azabicyclo[3.3.0]octane derivative 7 can be fonnally envisioned to arise from a cyclization leading to the cyclopentadiene derivative 15 followed by an isomerization. For both complexes 6 and 9 this cyclization occurs without CO insertion and leads exclusively to the fonnation of five-membered ring annulated Scheme II
MeaSi\ H'NJ
OMe
(CO)scr~
SiMea
~A1
3) 2 Bull, THF, -78 DC 4) 2 TMSCI, THF, -78 DC
A1
"'N...,r-==-
12h
57 % 60 %
A1
11 1) .HC':";--=
(CO)sCr
7
b H... N
H2 N
E120. -78 DC 2) nBuLi
J
2 -
1r(co)s
SiMe3 C6H6. 87 DC 12h
3) 2 Bull, THF, -78 DC 4) 2 TMSCI. THF. -78 DC
8
~m H
.&
13
~
H
Cr(CO)s
MeaSi
_O~C~ A1~ 12
3:ri 10 40 0/0
950% (E:Z.1:1)
R1
12h
:~
A1
(COl'C'b
A1
~6H6' 80 DC
7'
'\
(CO)scr~
OMe
(Co)scr~ 6-Z 27%
C6H6. 88 DC \
-
N-H
6-E 35%
5 H
'"
+
(CO)sCr=<
-~ H
MeaSi~ ~
A1~N
H 14
H
...,.
15
~
H
-7
8755
products. I I The structures 12 and 14 in Scheme II are not meant to imply a mechanism but only to define the transformation. A completely different result is observed if the tether between the amino group and the alkyne function has one additional methylene group. The complexes 16 and 17 were prepared from the methoxyl complex 5 by aminolysis with the proper l-amin0-4-pentynyl derivative. These complexes were obtained predominantely as the E-isomer but when the terminal alkynyl complex 17 was silylated the Z-isomer was the predominant product. 12 It was surprising to find that complex 16 was a stable complex since its lower homolog 11 could not be isolated in pure form. The thermolysis of the three complexes 16 - 18 each gave the CO inserted six• membered ring annulated product in the form of the 6-hydroxytetrahydroquinolines 19 - 21. In each case these were the major products in the crude reaction mixture and in no case were five-membered ring products identified from these reactions. Only in the case of the complex 18 were small amounts of silica gel mobile side• products observed in the crude reaction mixture but these compounds were not identified. Sc;heme III OMe
(CO)5Cr~
H2N-I\
H
H
El;zO, ·78 "C '\\
R
Ph S benzene (O.25M)
85 "C. 12·17h
(CO)sCrJ~ ~
R
Ph 16 R. Ph 500/0E:Z.11:1 17 R. H 90%E:Z.3.5:1 R
1) 2 BuU. THF, ·78°C 2) 2 TMSCI. THF. ·78 't
(co)~r~~jMe3 Ph 18 54'" E:Z _1:15.S
H:CO Ph
1.&
,
H 19 R. Ph 59 % 20 R.H 22% 21 R. SiMll3 29'"
15
19 ·21
The dramatic difference in chemoselectivity for the two-carbon and three-carbon tethered complexes 6 and 18. which are otherwise identical. is not precedented for intramolecular reactions of carbene complexes with alkynes. There is one example of a switch from six to five-membered ring products with the same tether-link change for amino complexes but this involved aryl complexes of different electronic properties. 13 •14 There is also one example of a tether induced change in distribution from a CO inserted product to an alkyne inserted product in an intramolecular two-alkyne annulation. 15 Based on the best evidence to date on the mechanism of these reactions. it is likely that the tether size is exerting its influence on the relative rates in which the" 1.,,3_ vinyl carbene complexed intermediate 22 cylcizes to give the five-membered ring annulated product 15 or undergoes CO insertion to give the vinyl ketene complex 23. 11 Further experiments are planned to determine the origin of the chemoselective differences observed in these reactions and to define the scope of their synthetic utility.l6 References I. For a recent review. see Wulff. W. D. in "Comprehensive Organometallic Chemistry n". Abel. E. W.; Stone. F. G. A.; Wilkinson. G.• Eds.• Pergamon Press. 1995. Vol 12. 2. a) Hugel. H. M.; Kennaway. D. J. Org. Prep. Proc. Int. 1995.27.1. b) Levy, A. D.; van de Kar. L. D. Life Sci. 1992,5 J, 83. c) Glennon, R. A. J. Med. Chern. 1987,30, l. 3. Wulff, W. D.; Gilbert, A. M.; Hsung, R. P.; Rahm. A. J. Org. Chern., 1995,60,4566. 4. Preparation of l-amino-3-butyne was accomplished in 54 % yield by a Curtius rearrangement by the procedure of Nageli where trimethylsilyl azide is substituted for sodium azide: Moller. F. in "Methoden der Organishcen Chemie". Houben-Weyl, Georg Thieme Verlag. 1957. Vol 11/1, p. 865.
8756
5. 6.
7. 8.
9. 10. II. 12. 13. 14. 15. 16.
Aumann, R.; Heinen, H. Chem. Ber., 1987,120, 537. a) Semmelhack, M. F.; Bozell, J. J.; Keller, L.; Sato, T.; Spiess, E.; Wulff, W. D.; Zask, A. Tetrahedron 1985,41, 5803. b) Wulff, W. D.; McCallum, 1. S.; Kunng, F.-A. J. Am. Chem. Soc. 1988, llO, 7419. c) Gross, M. F.; Finn, M. G. J. Am. Chem. Soc. 1994, ll6, 10921. Anderson, B. A.; Wulff, W. D.; Rahm, A. J. Am. Chem. Soc. 1993,ll5, 4602. All new compounds were fully characterized. The following data is for selected compounds from this work. 6.Z: orange solid, mp. 82 - 87°C; IH NMR (500 MHz, CDCI3) l) 0.20 (s, 9H), 2.79 (t, 2H, J = 6.1 Hz), 4.18 (q, 2H, J = 5.9 Hz), 6.31 (d, tH, J = 15.7 Hz), 7.33 (d, tH, J = 7.0 Hz), 7.37 (t, 2H, J = 7.35 Hz), 7.46 (d, 2H, J = 7.6 Hz), 7.55 (d, IH, 1 = 15.7 Hz), 9.04 (broad s, tH); 13C NMR (75 MHz, CDCI3) l) -0.1, 20.6,50.4, 89.5, 101.6, 123.7, 127.7, 128.9, 129.2, 135.0, 141.3,217.4, 223.3,268.5; IR (thin film) 2178w, 2054m, 1974 shoulder, 1913s cm- 1; mass spectrum (EO mlz (% rei intensity) 447 (M+, 4). 6·E: yellow-brown solid, mp. 67 - 70°C; IH NMR (500 MHz, CDCI3) l) 0.22 (s, 9H), 2.65 (t, 2H, J = 5.3 Hz), 3.71 (q, 2H, J = 5.7 Hz), 6.75 (d, tH, J = 16.1 Hz), 7.21 (d, lH, J = 16.4 Hz), 7.33 (d, lH, 1 = 6.9 Hz), 7.37 (t, 2H, J = 6.9 Hz), 7.47 (d, 2H, J = 7.1 Hz), 8.94 (broad s, IH); 13C NMR (75 MHz, CDCI3) l) -0.3, 20.5, 47.3, 94.0, 100.4, 127.3, 128.9, 129.3, 132.9, 135.4, 135.6,217.6,223.0,274.8; IR (thin film) 2178w, 2054m, 1973shoulder, 1913s cm- I ; mass spectrum (EI) mlz (% rei intensity) 447 (M+, 6). 7: yellow oil, IH NMR (500 MHz, CDCI3) l) -0.08 (s, 9H), 2.53 (dd, lH, J = 19.0 Hz, 1 = 1.4 Hz), 2.64 - 2.59 (m, 2H), 3.18 (dd, lH,l 19.3 HZ,I = 7.1 Hz), 4.35 - 4.30 (m, 2H), 4.47 (broad s, lH), 7.09 (d, 2H, 1 = 7.8 Hz), 7.22 (d, lH, J - 7.6 Hz), 7.29 (t, 2H, J = 7.0 Hz); 13C NMR (75 MHz, CDCI3) B -1.8, 24.3, 37.5, 59.7, 75.2, 127.1,127.5, 128.7, 143.2, 152.1,158.0,197.4,214.8,220.3,; IR (thin film) 2053w, 1922s em-I; mass spectrum (EI) mlz (% rei intensity) 447 (M+, 12); Anal Caled for C21H2INOSSiCr: C, 56.37; H, 4.73; N, 3.13. Found: C, 56.69; H, 4.75; N, 3.14. 18: orange oil, IH NMR (SOO MHz, CDCI3) l) 0.15 (s, 9H), 2.08 (t, 2H, 1 = 6.7 Hz), 2.52 (t, 2H, J = 6.5 Hz), 4.19 (q, 2H, J = 6.5 Hz), 6.25 (d, lH, J = IS.7 Hz), 7.45 - 7.22 (m, SH), 7.50 (d, lH, J = IS.8 Hz), 9.99 (broad s, lH),; 13C NMR (7S MHz, CDCI3) l) -0.04, 17.8, 28.0, 52.5, 87.2, 104.8, 124.0, 127.5, 127.6, 128.9, 129.1, 141.2, 217.5, 223.4,267.9; IR (thin film) 2174w, 2054s, 1973m, 1916s, ; mass spectrum (EI) mlz (% rei intensity) 461 (M+, 0.12), 433 (M+·CO, 10); Anal Calcd for C22H23NOsSiCr: C, 57.26; H, S.02; N, 3.03. Found: C, 57.22; H, 4.91; N, 3.52. 21: biege solid, mp. 103 - 104°C; IH NMR (SOO MHz, CDCI3) /)0.41 (s, 9H), 1.96 (p, 2H, J = 5.9 Hz), 2.89 (t, 2H, J = 6.5 Hz), 3.25 (t, 2H, J = 5.3 Hz), 4.87 (s, tH), 6.43 (s, lH), 7.34 (t, lH, J = 6.9 Hz), 7.39 - 7.47 (m, 4H); 13C NMR (7S MHz, CDCI3) B 2.7, 23.0, 28.7, 41.8, 118.4, 124.4, 126.4, 127.6, 128.3, 129.2, 129.3, 137.6, 138.1, 149.5; mass spectrum (EI) mlz (% rei intensity) 297 (M+, 1(0). Chan, K. S.; Peterson, G. A.; Brandvold, T. A.; Faron, K. L.; Challener, C. A.; Hyldahl, C.; Wulff, W. D. J. Organometa/. Chem. 1987,334,9. Connor, 1. A.; Rose, P. D. J. Organometal. Chem. 1972,46, 329. For a recent discussion and citations to the literature, see: Wulff, W. D.; Bax, B. M.; Brandvold, T. A.; Chan, K. S.; Gilbert, A. M.; Hsung, R. P. Organometa//ics 1994,13, 102. The E : Z ratio for the initial adducts from the reaction of complex 5 with l-amino-3-butyne prior to silylation is 2 : 1. Dotz, K. H.; Schaefer, T. 0.; Harms, K. Synthesis 1992, 146. Chelain, E.; Parlier, A.; Audouin, M.; Rudler, H.; Daran, J. C.; Vaissermann, 1. J. Am. Chem. Soc. 1993, /15, 10568. Bao, 1.; Wulff, W. D.; Dragisich, V.; Wenglowsky, S.; Ball, R. G. J. Am. Chem. Soc. 1994, 116, 7616. This work was supported by a grant from NIH (GM 33589).
(Received in USA 14 September 1995; revised 3 October 1995; accepted 4 October 1995)
TetYaMdron Leiters. Vol. 36, No. 48, pp. 87~3·8756, 199~ Elsevier Science lid Prinled in Greal Brilain
Pergamon
0040-4039195 $9.50+0.00
0040-4039(95)01923-5
Azabicyclo[3.3.0]octanes and 6·Hydroxytetrahydroquinolines from Intramolecular Reactions of Alkenyl(amino)carbene Complexes with Alkynes. Annette Rahm and William D. WullT* Department of Chemislly The University of Chicago Chicago. Illinois 60637
Abstract: The intramolecular reactions of alkenyl substituted amino carbcne complcxes with alkyne functional groups tethered through the nitrogen substituent of the carbene carbon are examined. These cyclizations were expected 10 occur with incorporation of CO 10 bicyclic nitrogcn hctrocyclic compounds containing a phenol function. This was found 10 be the case with complexes with three-carbon spacers between the nitrogen and alkyne where 6-hydroxytetrahydroquinolines were produced. In contrasl, complexes with two-carbon spacers gave )·azabicyclo[J,3.0)octanes that resulted from cyclization without CO insertion.
Much is known about the reactions of Fischer carbene complexes with alkynes) but the intramolecular reactions of alkenyl(arnino) carbene complexes with alkynes have not been examined. Despite the very large number of products that could potentially result from this reaction,} the possiblity that this reaction could provide a new route to 5-hydroxyindoles was sufficiently attractive to warrant an investigation given the biological importance of this class of molecules. 2 Evidence to suppon the expectation that the intramolecular reaction of complex 1 will produce 5-hydroxyindolines comes from the recent finding that alkenyl(amino) carbene complexes will react with terminal alkynes in an intermolecular fashion to give 4-aminophenol products of the type 4 in moderate to good yields.3 The simplest amine tethered alkyne that could be used is l-amino-3-butyne4 and this unit was introduced by the standard aminolysis reaction. The styryl carbene complex 6 was prepared in 63 % yield from the methoxyl complex S5 by treatment with one equivalent of the amine at ·78 0C and then warming to 25 OC for 15 Seheme I
H~3 A2~: A'
H
2
benzene
H»~'M' R'
4
8753
Me
39·64%
8754
minutes. The tenninal alkyne function that was obtained in the initial product of this reaction was silylated to give complex 6 since it is known in intramolecular reactions of alkoxy carbene complexes with alkynes that the yields are significantly lower with a tenninal alkyne function. 6 The alkenyl amino carbene complex 6 was obtained as a 1.3 : 1 mixture of geometrical isomers due to hindered rotation about the nitrogen-carbene carbon bond and which were assigned on the basis of their NMR spectral data? as the E and Z isomers, respectively.8 These isomers were readily separated by chromatography on silica gel with a 1: 1: 10 mixture of ether:CH2CI2:hexane and their thennolysis was studied independently. The geometry of the carbene complex 6 did not have an effect on the intramolecular reaction with the alkyne unit as both isomers gave the same product in the same yield, however, the product observed was not a 5-hydroxyindoline, but rather the 1• azabicyclo[3.3.0]octane chromium carbonyl complex 7. The same outcome was observed for the carbene complex 9 which was obtained by aminolysis of complex 89 and thennolyzed as a 1:1 mixture of isomers as a 0.25 M solution in benzene to give the tricyclic imine complex 10. While the complex 11 could be prepared, this material was unstable and decomposition during purification was readily evident. Several compounds were produced in the decomposition which have not yet been identified but do not appear to involve carbon-carbon bond fonnation between the carbene carbon and the alkyne function and do not include cinnamaldehyde or 1• amino-3-butyne which may be expected from the decomposition of secondary amino carbene complexes. to The fonnation of the azabicyclo[3.3.0]octane derivative 7 can be fonnally envisioned to arise from a cyclization leading to the cyclopentadiene derivative 15 followed by an isomerization. For both complexes 6 and 9 this cyclization occurs without CO insertion and leads exclusively to the fonnation of five-membered ring annulated Scheme II
MeaSi\ H'NJ
OMe
(CO)scr~
SiMea
~A1
3) 2 Bull, THF, -78 DC 4) 2 TMSCI, THF, -78 DC
A1
"'N...,r-==-
12h
57 % 60 %
A1
11 1) .HC':";--=
(CO)sCr
7
b H... N
H2 N
E120. -78 DC 2) nBuLi
J
2 -
1r(co)s
SiMe3 C6H6. 87 DC 12h
3) 2 Bull, THF, -78 DC 4) 2 TMSCI. THF. -78 DC
8
~m H
.&
13
~
H
Cr(CO)s
MeaSi
_O~C~ A1~ 12
3:ri 10 40 0/0
950% (E:Z.1:1)
R1
12h
:~
A1
(COl'C'b
A1
~6H6' 80 DC
7'
'\
(CO)scr~
OMe
(Co)scr~ 6-Z 27%
C6H6. 88 DC \
-
N-H
6-E 35%
5 H
'"
+
(CO)sCr=<
-~ H
MeaSi~ ~
A1~N
H 14
H
...,.
15
~
H
-7
8755
products. I I The structures 12 and 14 in Scheme II are not meant to imply a mechanism but only to define the transformation. A completely different result is observed if the tether between the amino group and the alkyne function has one additional methylene group. The complexes 16 and 17 were prepared from the methoxyl complex 5 by aminolysis with the proper l-amin0-4-pentynyl derivative. These complexes were obtained predominantely as the E-isomer but when the terminal alkynyl complex 17 was silylated the Z-isomer was the predominant product. 12 It was surprising to find that complex 16 was a stable complex since its lower homolog 11 could not be isolated in pure form. The thermolysis of the three complexes 16 - 18 each gave the CO inserted six• membered ring annulated product in the form of the 6-hydroxytetrahydroquinolines 19 - 21. In each case these were the major products in the crude reaction mixture and in no case were five-membered ring products identified from these reactions. Only in the case of the complex 18 were small amounts of silica gel mobile side• products observed in the crude reaction mixture but these compounds were not identified. Sc;heme III OMe
(CO)5Cr~
H2N-I\
H
H
El;zO, ·78 "C '\\
R
Ph S benzene (O.25M)
85 "C. 12·17h
(CO)sCrJ~ ~
R
Ph 16 R. Ph 500/0E:Z.11:1 17 R. H 90%E:Z.3.5:1 R
1) 2 BuU. THF, ·78°C 2) 2 TMSCI. THF. ·78 't
(co)~r~~jMe3 Ph 18 54'" E:Z _1:15.S
H:CO Ph
1.&
,
H 19 R. Ph 59 % 20 R.H 22% 21 R. SiMll3 29'"
15
19 ·21
The dramatic difference in chemoselectivity for the two-carbon and three-carbon tethered complexes 6 and 18. which are otherwise identical. is not precedented for intramolecular reactions of carbene complexes with alkynes. There is one example of a switch from six to five-membered ring products with the same tether-link change for amino complexes but this involved aryl complexes of different electronic properties. 13 •14 There is also one example of a tether induced change in distribution from a CO inserted product to an alkyne inserted product in an intramolecular two-alkyne annulation. 15 Based on the best evidence to date on the mechanism of these reactions. it is likely that the tether size is exerting its influence on the relative rates in which the" 1.,,3_ vinyl carbene complexed intermediate 22 cylcizes to give the five-membered ring annulated product 15 or undergoes CO insertion to give the vinyl ketene complex 23. 11 Further experiments are planned to determine the origin of the chemoselective differences observed in these reactions and to define the scope of their synthetic utility.l6 References I. For a recent review. see Wulff. W. D. in "Comprehensive Organometallic Chemistry n". Abel. E. W.; Stone. F. G. A.; Wilkinson. G.• Eds.• Pergamon Press. 1995. Vol 12. 2. a) Hugel. H. M.; Kennaway. D. J. Org. Prep. Proc. Int. 1995.27.1. b) Levy, A. D.; van de Kar. L. D. Life Sci. 1992,5 J, 83. c) Glennon, R. A. J. Med. Chern. 1987,30, l. 3. Wulff, W. D.; Gilbert, A. M.; Hsung, R. P.; Rahm. A. J. Org. Chern., 1995,60,4566. 4. Preparation of l-amino-3-butyne was accomplished in 54 % yield by a Curtius rearrangement by the procedure of Nageli where trimethylsilyl azide is substituted for sodium azide: Moller. F. in "Methoden der Organishcen Chemie". Houben-Weyl, Georg Thieme Verlag. 1957. Vol 11/1, p. 865.
8756
5. 6.
7. 8.
9. 10. II. 12. 13. 14. 15. 16.
Aumann, R.; Heinen, H. Chem. Ber., 1987,120, 537. a) Semmelhack, M. F.; Bozell, J. J.; Keller, L.; Sato, T.; Spiess, E.; Wulff, W. D.; Zask, A. Tetrahedron 1985,41, 5803. b) Wulff, W. D.; McCallum, 1. S.; Kunng, F.-A. J. Am. Chem. Soc. 1988, llO, 7419. c) Gross, M. F.; Finn, M. G. J. Am. Chem. Soc. 1994, ll6, 10921. Anderson, B. A.; Wulff, W. D.; Rahm, A. J. Am. Chem. Soc. 1993,ll5, 4602. All new compounds were fully characterized. The following data is for selected compounds from this work. 6.Z: orange solid, mp. 82 - 87°C; IH NMR (500 MHz, CDCI3) l) 0.20 (s, 9H), 2.79 (t, 2H, J = 6.1 Hz), 4.18 (q, 2H, J = 5.9 Hz), 6.31 (d, tH, J = 15.7 Hz), 7.33 (d, tH, J = 7.0 Hz), 7.37 (t, 2H, J = 7.35 Hz), 7.46 (d, 2H, J = 7.6 Hz), 7.55 (d, IH, 1 = 15.7 Hz), 9.04 (broad s, tH); 13C NMR (75 MHz, CDCI3) l) -0.1, 20.6,50.4, 89.5, 101.6, 123.7, 127.7, 128.9, 129.2, 135.0, 141.3,217.4, 223.3,268.5; IR (thin film) 2178w, 2054m, 1974 shoulder, 1913s cm- 1; mass spectrum (EO mlz (% rei intensity) 447 (M+, 4). 6·E: yellow-brown solid, mp. 67 - 70°C; IH NMR (500 MHz, CDCI3) l) 0.22 (s, 9H), 2.65 (t, 2H, J = 5.3 Hz), 3.71 (q, 2H, J = 5.7 Hz), 6.75 (d, tH, J = 16.1 Hz), 7.21 (d, lH, J = 16.4 Hz), 7.33 (d, lH, 1 = 6.9 Hz), 7.37 (t, 2H, J = 6.9 Hz), 7.47 (d, 2H, J = 7.1 Hz), 8.94 (broad s, IH); 13C NMR (75 MHz, CDCI3) l) -0.3, 20.5, 47.3, 94.0, 100.4, 127.3, 128.9, 129.3, 132.9, 135.4, 135.6,217.6,223.0,274.8; IR (thin film) 2178w, 2054m, 1973shoulder, 1913s cm- I ; mass spectrum (EI) mlz (% rei intensity) 447 (M+, 6). 7: yellow oil, IH NMR (500 MHz, CDCI3) l) -0.08 (s, 9H), 2.53 (dd, lH, J = 19.0 Hz, 1 = 1.4 Hz), 2.64 - 2.59 (m, 2H), 3.18 (dd, lH,l 19.3 HZ,I = 7.1 Hz), 4.35 - 4.30 (m, 2H), 4.47 (broad s, lH), 7.09 (d, 2H, 1 = 7.8 Hz), 7.22 (d, lH, J - 7.6 Hz), 7.29 (t, 2H, J = 7.0 Hz); 13C NMR (75 MHz, CDCI3) B -1.8, 24.3, 37.5, 59.7, 75.2, 127.1,127.5, 128.7, 143.2, 152.1,158.0,197.4,214.8,220.3,; IR (thin film) 2053w, 1922s em-I; mass spectrum (EI) mlz (% rei intensity) 447 (M+, 12); Anal Caled for C21H2INOSSiCr: C, 56.37; H, 4.73; N, 3.13. Found: C, 56.69; H, 4.75; N, 3.14. 18: orange oil, IH NMR (SOO MHz, CDCI3) l) 0.15 (s, 9H), 2.08 (t, 2H, 1 = 6.7 Hz), 2.52 (t, 2H, J = 6.5 Hz), 4.19 (q, 2H, J = 6.5 Hz), 6.25 (d, lH, J = IS.7 Hz), 7.45 - 7.22 (m, SH), 7.50 (d, lH, J = IS.8 Hz), 9.99 (broad s, lH),; 13C NMR (7S MHz, CDCI3) l) -0.04, 17.8, 28.0, 52.5, 87.2, 104.8, 124.0, 127.5, 127.6, 128.9, 129.1, 141.2, 217.5, 223.4,267.9; IR (thin film) 2174w, 2054s, 1973m, 1916s, ; mass spectrum (EI) mlz (% rei intensity) 461 (M+, 0.12), 433 (M+·CO, 10); Anal Calcd for C22H23NOsSiCr: C, 57.26; H, S.02; N, 3.03. Found: C, 57.22; H, 4.91; N, 3.52. 21: biege solid, mp. 103 - 104°C; IH NMR (SOO MHz, CDCI3) /)0.41 (s, 9H), 1.96 (p, 2H, J = 5.9 Hz), 2.89 (t, 2H, J = 6.5 Hz), 3.25 (t, 2H, J = 5.3 Hz), 4.87 (s, tH), 6.43 (s, lH), 7.34 (t, lH, J = 6.9 Hz), 7.39 - 7.47 (m, 4H); 13C NMR (7S MHz, CDCI3) B 2.7, 23.0, 28.7, 41.8, 118.4, 124.4, 126.4, 127.6, 128.3, 129.2, 129.3, 137.6, 138.1, 149.5; mass spectrum (EI) mlz (% rei intensity) 297 (M+, 1(0). Chan, K. S.; Peterson, G. A.; Brandvold, T. A.; Faron, K. L.; Challener, C. A.; Hyldahl, C.; Wulff, W. D. J. Organometa/. Chem. 1987,334,9. Connor, 1. A.; Rose, P. D. J. Organometal. Chem. 1972,46, 329. For a recent discussion and citations to the literature, see: Wulff, W. D.; Bax, B. M.; Brandvold, T. A.; Chan, K. S.; Gilbert, A. M.; Hsung, R. P. Organometa//ics 1994,13, 102. The E : Z ratio for the initial adducts from the reaction of complex 5 with l-amino-3-butyne prior to silylation is 2 : 1. Dotz, K. H.; Schaefer, T. 0.; Harms, K. Synthesis 1992, 146. Chelain, E.; Parlier, A.; Audouin, M.; Rudler, H.; Daran, J. C.; Vaissermann, 1. J. Am. Chem. Soc. 1993, /15, 10568. Bao, 1.; Wulff, W. D.; Dragisich, V.; Wenglowsky, S.; Ball, R. G. J. Am. Chem. Soc. 1994, 116, 7616. This work was supported by a grant from NIH (GM 33589).
(Received in USA 14 September 1995; revised 3 October 1995; accepted 4 October 1995)