Application of a new family of P,N ligands to the highly enantioselective hydrosilylation of aryl alkyl and dialkyl ketones

Angewandte Chemie - International Edition

Volumn 41, Issue 20, 2002, Pages 3892-3894

  Tao, Beata ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Asymmetric catalysis; Hydrosilylation; P,N ligands; Reduction; Rhodium

Indexed keywords

CATALYSIS; HYDROGENATION; KETONES; NITROGEN; STEREOCHEMISTRY;

LIGANDS;

PHOSPHORUS;

ALKYL ARYL KETONE; KETONE DERIVATIVE; NITROGEN DERIVATIVE; PHOSPHORUS DERIVATIVE; RHODIUM;

ANALYTIC METHOD; ARTICLE; CATALYSIS; ENANTIOSELECTIVITY; HYDROGENATION; REACTION ANALYSIS; REDUCTION; SILYLATION;

EID: 0037131584     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20021018)41:20<3892::AID-ANIE3892>3.0.CO;2-A     Document Type: Article

References (30)

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6. a) Asymmetric isomerization of allylic alcohols: K. Tanaka. S. Qiao, M. Tobisu, M. M.-C. Lo, G. C. Fu, J. Am. Chem. Soc. 2000, 122, 9870-9871; K. Tanaka, G. C. Fu, J. Org. Chem. 2001, 66. 8177-8186
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11. 4;
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13. c) the stereoselectivity does not appear to be dependent on the concentration.
14. In the case of isopropyl phenyl ketone, we observe good enantiose-lectivity (86% ee), but a very slow reaction rate (14% conversion after 5 days with a 5% catalyst loading).
15. The modest yield is due to the volatility of the product.
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19. For examples of asymmetric hydrosilylation catalysts that are effective for aryl alkyl ketones but relatively ineffective for dialkyl ketones, see: a) H. Mimoun, J. Yves de Saint Laumer, L. Giannini, R. Scopelliti, C. Floriani, J. Am. Chem. Soc. 1999, 121, 6158-6166; b) J. Yun, S. L. Buchwald, J. Am. Chem. Soc. 1999, 121, 5640-5644.
20. For examples of asymmetric hydrosilylation catalysts that are effective for aryl alkyl ketones but relatively ineffective for dialkyl ketones, see: a) H. Mimoun, J. Yves de Saint Laumer, L. Giannini, R. Scopelliti, C. Floriani, J. Am. Chem. Soc. 1999, 121, 6158-6166; b) J. Yun, S. L. Buchwald, J. Am. Chem. Soc. 1999, 121, 5640-5644.
21. Until now, taking into account both scope and enantioselectivity, the best catalysts for asymmetric hydrosilylations of dialkyl ketones were rhodium complexes of Ito's TRAP family of ligands: a) R. Kuwano, T. Uemura, M. Saitoh, Y. Ito, Tetrahedron Lett. 1999, 40, 1327-1330; b) R. Kuwano, M. Sawamura, J. Shirai, M. Takahashi, Y. Ito, Bull. Chem. Soc. Jpn. 2000, 73, 485-496. The Rh/TRAP catalysts provide good, but not exceptionally high, enantioselectivities for hydrosilylations of aryl alkyl ketones. See also: D. K. Heldmann, D. Seebach, Helv. Chim. Acta 1999, 82, 1096-1110; Y. Nishibayashi, K. Segawa, K. Ohe, S. Uemura, Organometallics 1995, 14, 5486-5487.
22. Until now, taking into account both scope and enantioselectivity, the best catalysts for asymmetric hydrosilylations of dialkyl ketones were rhodium complexes of Ito's TRAP family of ligands: a) R. Kuwano, T. Uemura, M. Saitoh, Y. Ito, Tetrahedron Lett. 1999, 40, 1327-1330; b) R. Kuwano, M. Sawamura, J. Shirai, M. Takahashi, Y. Ito, Bull. Chem. Soc. Jpn. 2000, 73, 485-496. The Rh/TRAP catalysts provide good, but not exceptionally high, enantioselectivities for hydrosilylations of aryl alkyl ketones. See also: D. K. Heldmann, D. Seebach, Helv. Chim. Acta 1999, 82, 1096-1110; Y. Nishibayashi, K. Segawa, K. Ohe, S. Uemura, Organometallics 1995, 14, 5486-5487.
23. Until now, taking into account both scope and enantioselectivity, the best catalysts for asymmetric hydrosilylations of dialkyl ketones were rhodium complexes of Ito's TRAP family of ligands: a) R. Kuwano, T. Uemura, M. Saitoh, Y. Ito, Tetrahedron Lett. 1999, 40, 1327-1330; b) R. Kuwano, M. Sawamura, J. Shirai, M. Takahashi, Y. Ito, Bull. Chem. Soc. Jpn. 2000, 73, 485-496. The Rh/TRAP catalysts provide good, but not exceptionally high, enantioselectivities for hydrosilylations of aryl alkyl ketones. See also: D. K. Heldmann, D. Seebach, Helv. Chim. Acta 1999, 82, 1096-1110; Y. Nishibayashi, K. Segawa, K. Ohe, S. Uemura, Organometallics 1995, 14, 5486-5487.
24. Until now, taking into account both scope and enantioselectivity, the best catalysts for asymmetric hydrosilylations of dialkyl ketones were rhodium complexes of Ito's TRAP family of ligands: a) R. Kuwano, T. Uemura, M. Saitoh, Y. Ito, Tetrahedron Lett. 1999, 40, 1327-1330; b) R. Kuwano, M. Sawamura, J. Shirai, M. Takahashi, Y. Ito, Bull. Chem. Soc. Jpn. 2000, 73, 485-496. The Rh/TRAP catalysts provide good, but not exceptionally high, enantioselectivities for hydrosilylations of aryl alkyl ketones. See also: D. K. Heldmann, D. Seebach, Helv. Chim. Acta 1999, 82, 1096-1110; Y. Nishibayashi, K. Segawa, K. Ohe, S. Uemura, Organometallics 1995, 14, 5486-5487.
25. 4.
26. Dialkyl ketones have proved to be very challenging substrates for asymmetric hydrogenation catalysts. a) For overviews, see: T. Ohkuma, R. Noyori in Comprehensive Asymmetric Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999, chap. 6.1: V. Fehring, R. Selke, Angew. Chem. 1998, 110, 1927-1930; Angew. Chem. Int. Ed. 1998, 37, 1827-1830; b) Q. Jiang, Y. Jiang, D. Xiao, P. Cao, X. Zhang, Angew. Chem. 1998, 110, 1203-1207; Angew. Chem. Int. Ed. 1998, 37, 1100-1103.
27. Dialkyl ketones have proved to be very challenging substrates for asymmetric hydrogenation catalysts. a) For overviews, see: T. Ohkuma, R. Noyori in Comprehensive Asymmetric Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999, chap. 6.1: V. Fehring, R. Selke, Angew. Chem. 1998, 110, 1927-1930; Angew. Chem. Int. Ed. 1998, 37, 1827-1830; b) Q. Jiang, Y. Jiang, D. Xiao, P. Cao, X. Zhang, Angew. Chem. 1998, 110, 1203-1207; Angew. Chem. Int. Ed. 1998, 37, 1100-1103.
28. Dialkyl ketones have proved to be very challenging substrates for asymmetric hydrogenation catalysts. a) For overviews, see: T. Ohkuma, R. Noyori in Comprehensive Asymmetric Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999, chap. 6.1: V. Fehring, R. Selke, Angew. Chem. 1998, 110, 1927-1930; Angew. Chem. Int. Ed. 1998, 37, 1827-1830; b) Q. Jiang, Y. Jiang, D. Xiao, P. Cao, X. Zhang, Angew. Chem. 1998, 110, 1203-1207; Angew. Chem. Int. Ed. 1998, 37, 1100-1103.
29. Dialkyl ketones have proved to be very challenging substrates for asymmetric hydrogenation catalysts. a) For overviews, see: T. Ohkuma, R. Noyori in Comprehensive Asymmetric Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999, chap. 6.1: V. Fehring, R. Selke, Angew. Chem. 1998, 110, 1927-1930; Angew. Chem. Int. Ed. 1998, 37, 1827-1830; b) Q. Jiang, Y. Jiang, D. Xiao, P. Cao, X. Zhang, Angew. Chem. 1998, 110, 1203-1207; Angew. Chem. Int. Ed. 1998, 37, 1100-1103.
30. Dialkyl ketones have proved to be very challenging substrates for asymmetric hydrogenation catalysts. a) For overviews, see: T. Ohkuma, R. Noyori in Comprehensive Asymmetric Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999, chap. 6.1: V. Fehring, R. Selke, Angew. Chem. 1998, 110, 1927-1930; Angew. Chem. Int. Ed. 1998, 37, 1827-1830; b) Q. Jiang, Y. Jiang, D. Xiao, P. Cao, X. Zhang, Angew. Chem. 1998, 110, 1203-1207; Angew. Chem. Int. Ed. 1998, 37, 1100-1103.