Enantioselective construction of quaternary stereogenic carbons by the Lewis base catalyzed additions of silyl ketene imines to aldehydes

Journal of the American Chemical Society

Volumn 129, Issue 48, 2007, Pages 14864-14865

  Denmark, Scott E ^a   Wilson, Tyler W ^a   Burk, Matthew T ^a   Heemstra Jr , John R ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; IMINE; LEWIS BASE; SILYL KETENE IMINE; UNCLASSIFIED DRUG;

ACYLATION; ADDITION REACTION; ALDOL REACTION; ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENANTIOSELECTIVITY; X RAY CRYSTALLOGRAPHY;

EID: 36849060666     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja077134y     Document Type: Article

References (23)

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3. (c) Denissova, I.; Barriault, L. Tetrahedron 2003, 59, 10105-10146.
4. (d) For a recent monograph, see: Quaternary Stereocenters: Challenges and Solutions for Organic Synthesis; Christoffers, J., Baro, A., Eds.; Wiley-VCH: Weinheim, Germany, 2005.
5. For reviews on catalytic asymmetric aldol reactions, see: (a) Carreira, E. M. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: New York, 1999; Chapter 29.1.
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7. (c) For a recent monograph, see: Modern Aldol Reactions; Mahrwald, R., Ed.; Wiley-VCH: Weinheim, Germany, 2004.
8. For a discussion on quaternary carbon synthesis via aldol reaction, see: ref 1d, Chapter 3.
9. However, studies on both N-alkyl and N-aryl ketene imines reveal a low barrier to racemization; see: (a) Jochims, J. C.; Lambrecht, J.; Burkert, U.; Zsolnai, L.; Huttner, G. Tetrahedron 1984, 40, 893-903.
10. (b) Lambrecht, J.; Gambke, B.; Seyerl, J.; Huttner, G.; Nell, G.; Herzberger, S.; Jochims, J. C. Chem. Ber. 1981, 114, 3751-3771.
11. For an example of this catalytic, enantioselective process, see: Kuwano, R.; Miyazaki, H.; Ito, Y. J. Organomet. Chem. 2000, 603, 18-29.
12. Tennant, G. In Comprehensive Organic Chemistry; Barton, D. H. R., Ollis, W. D., Sutherland, I. O., Eds.; Pergamon: New York, 1979; Vol. 2, pp 539-550.
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15. (a) For additions to aldehydes, see: Cazeau, P.; Llonch, J.-P.; Simonin-Dabescat, F.; Frainnet, E. J. Organomet. Chem. 1976, 105, 145-156.
16. (b) For additions to acid chlorides, see: Cazeau, P.; Llonch, J.-P.; Simonin-Dabescat, F.; Frainnet, E. J. Organomet. Chem. 1976, 105, 157-160.
17. Mermerian, A. H.; Fu, G. C. Angew. Chem., Int. Ed. 2005, 44, 949-952.
18. (a) Denmark, S. E.; Beutner, G. L. Angew. Chem., Int. Ed. 2007, in press.
19. (b) Denmark, S. E.; Fujimori, S. In Modern Aldol Reactions; Mahrwald, R., Ed.; Wiley-VCH: Weinheim, Germany, 2004; Vol. I, Chapter 7.
20. (c) Denmark, S. E.; Beutner, G. L.; Wynn, T.; Eastgate, M. D. J. Am. Chem. Soc. 2005, 127, 3774-3789.
21. The reduced reactivity of aliphatic aldehydes can be attributed to an unfavorable equilibrium that exists between the activated aldehyde complex and an inactive a-chlorotrichlorosilyl ether; see ref 10c.
22. The crystallographic coordinates of 6da have been deposited with the Cambridge Crystallographic Data Centre; deposition no. 659734. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; www.ccdc.cam.ac.uk/conts/retrieving.html or deposit@ccdc.cam.ac.uk.
23. Preliminary results from reactions of SKIs with α,β- unsaturated aldehydes show exclusive 1,4-addition with moderate diastereoselectivity.