Highly enantioselective imine hydrosilylation using (S,S)-ethylenebis(η5-tetrahydroindenyl)titanium difluoride

Journal of the American Chemical Society

Volumn 118, Issue 28, 1996, Pages 6784-6785

  Verdaguer, Xavier ^a   Lange, Udo E W ^a   Reding, Matthew T ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

SILANE DERIVATIVE;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029990507     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960808c     Document Type: Article

References (38)

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8. 2 reacts with a silane at room temperature: Xin, S.; Aitken, C.; Harrod, J. F.; Mu, Y. Can. J. Chem. 1990, 68, 471.
9. For examples of titanium(III) hydrides and silyl titanium hydrides, see: (a) Xin, S.; Harrod, J. F.; Samuel, E. J. Am. Chem. Soc. 1994, 116. 11562. (b) Wolf, J. M.; Meetsma, A.; Teuben, J. H. Organometallics 1995. 14, 5466. (c) Harrod, J. H.; Yun, S. S. Organometallics 1987, 6, 1381. (d) Spaltenstein, E.; Palma, P.; Kreutzer, K. A.; Willoughby, C. A.; Davis, W. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 10308.
10. For examples of titanium(III) hydrides and silyl titanium hydrides, see: (a) Xin, S.; Harrod, J. F.; Samuel, E. J. Am. Chem. Soc. 1994, 116. 11562. (b) Wolf, J. M.; Meetsma, A.; Teuben, J. H. Organometallics 1995. 14, 5466. (c) Harrod, J. H.; Yun, S. S. Organometallics 1987, 6, 1381. (d) Spaltenstein, E.; Palma, P.; Kreutzer, K. A.; Willoughby, C. A.; Davis, W. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 10308.
11. For examples of titanium(III) hydrides and silyl titanium hydrides, see: (a) Xin, S.; Harrod, J. F.; Samuel, E. J. Am. Chem. Soc. 1994, 116. 11562. (b) Wolf, J. M.; Meetsma, A.; Teuben, J. H. Organometallics 1995. 14, 5466. (c) Harrod, J. H.; Yun, S. S. Organometallics 1987, 6, 1381. (d) Spaltenstein, E.; Palma, P.; Kreutzer, K. A.; Willoughby, C. A.; Davis, W. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 10308.
12. For examples of titanium(III) hydrides and silyl titanium hydrides, see: (a) Xin, S.; Harrod, J. F.; Samuel, E. J. Am. Chem. Soc. 1994, 116. 11562. (b) Wolf, J. M.; Meetsma, A.; Teuben, J. H. Organometallics 1995. 14, 5466. (c) Harrod, J. H.; Yun, S. S. Organometallics 1987, 6, 1381. (d) Spaltenstein, E.; Palma, P.; Kreutzer, K. A.; Willoughby, C. A.; Davis, W. A.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 10308.
13. 2 was reported: Kiplinger, J. L.; Richmond, T. G. J. Am. Chem. Soc. 1996, 118, 1805.
14. 2 is a crystalline, air-stable yellow-orange solid and was prepared from the corresponding dichloride derivative in one step, see: (a) Schäfer, A.; Karl, E.; Zsolnai, L.; Gottfried, H.; Brintzinger, H. H. J. Organomet. Chem. 1987, 328, 87. (b) Bruce, P. M.; Kingston, B. M.; Lappert, M. F.; Spalding, T. R.; Srivastava, R. C. J. Chem. Soc. (A), 1969. 2106.
15. 2 is a crystalline, air-stable yellow-orange solid and was prepared from the corresponding dichloride derivative in one step, see: (a) Schäfer, A.; Karl, E.; Zsolnai, L.; Gottfried, H.; Brintzinger, H. H. J. Organomet. Chem. 1987, 328, 87. (b) Bruce, P. M.; Kingston, B. M.; Lappert, M. F.; Spalding, T. R.; Srivastava, R. C. J. Chem. Soc. (A), 1969. 2106.
16. (a) 1:base:MeOH = 1:4:4.
17. 1BuONa were all successfully used as bases.
18. The product silylamines could be observed (NMR) but were never isolated due to their lability.
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24. 3 were distilled and stored in an inert atmosphere.
25. 3 were distilled and stored in an inert atmosphere.
26. 3 were distilled and stored in an inert atmosphere.
27. 3 were distilled and stored in an inert atmosphere.
28. 3 were distilled and stored in an inert atmosphere.
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30. 3-Si-F) = 166 kcal/mol, see: (a) Connor, J. A. Top. Curr. Chem. 1977, 71, 71. (b) Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701. (c) Walsh, R. in The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons: New York, 1989.
31. 3-Si-F) = 166 kcal/mol, see: (a) Connor, J. A. Top. Curr. Chem. 1977, 71, 71. (b) Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701. (c) Walsh, R. in The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons: New York, 1989.
32. 3-Si-F) = 166 kcal/mol, see: (a) Connor, J. A. Top. Curr. Chem. 1977, 71, 71. (b) Schock, L. E.; Marks, T. J. J. Am. Chem. Soc. 1988, 110, 7701. (c) Walsh, R. in The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons: New York, 1989.
33. To our knowledge accurate bond energies for Ti-H have not been reported; therefore, a complete balanced thermochemical calculation is not possible.
34. For examples of base-catalyzed dehydrocondensation of silanes with alcohols, see: (a) Lukevics, E.; Dzintara, M. J. Organomet. Chem. 1984, 271, 307. (b) Gilman, H.; Dunn, G. E.; Hartzfeld, H.; Smith, A. G. J. Am. Chem. Soc. 1955, 77, 1287. (c) Bazant, V.; Chvalovsky, V.; Rathousky, J. In Organosilicon Compounds; Publishing House of the Czechoslovak Academy of Science: Prague, 1965; pp 54-56.
35. For examples of base-catalyzed dehydrocondensation of silanes with alcohols, see: (a) Lukevics, E.; Dzintara, M. J. Organomet. Chem. 1984, 271, 307. (b) Gilman, H.; Dunn, G. E.; Hartzfeld, H.; Smith, A. G. J. Am. Chem. Soc. 1955, 77, 1287. (c) Bazant, V.; Chvalovsky, V.; Rathousky, J. In Organosilicon Compounds; Publishing House of the Czechoslovak Academy of Science: Prague, 1965; pp 54-56.
36. For examples of base-catalyzed dehydrocondensation of silanes with alcohols, see: (a) Lukevics, E.; Dzintara, M. J. Organomet. Chem. 1984, 271, 307. (b) Gilman, H.; Dunn, G. E.; Hartzfeld, H.; Smith, A. G. J. Am. Chem. Soc. 1955, 77, 1287. (c) Bazant, V.; Chvalovsky, V.; Rathousky, J. In Organosilicon Compounds; Publishing House of the Czechoslovak Academy of Science: Prague, 1965; pp 54-56.
37. Woo, H-G.; Tilley, T. D. J. Am. Chem. Soc. 1989, 111, 8043.
38. 13b