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Synlett 2010(11): 1723-1728  
DOI: 10.1055/s-0029-1219963
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© Georg Thieme Verlag Stuttgart ˙ New York

Construction of Quaternary Stereogenic Carbon Centers by the Lewis Base Catalyzed Conjugate Addition of Silyl Ketene Imines to α,β-Unsaturated Aldehydes and Ketones

Scott E. Denmark*, Tyler W. Wilson
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, IL 61801, USA
Fax: +1(217)3333984; e-Mail: sdenmark@illinois.edu;
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Publication History

Received 11 May 2010
Publication Date:
10 June 2010 (online)

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Abstract

Highly site-selective Mukaiyama-Michael additions of silyl ketene imines to α,β-unsaturated aldehydes and ketones are described. The combination of silicon tetrachloride and a chiral bisphosphoramide provides an effective catalyst system for promoting the addition of silyl ketene imines to a variety of aromatic enals with high site selectivity and moderate to good diastereo- and enantioselectivity.

Key words

Lewis base - asymmetric catalysis - Michael addition - aldehydes - quaternary carbon

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See ref. 15j.

17

For recent preparation of SKIs, see ref .10.

18

For example, the observed selectivity could result from a single catalyst-enone complex if reaction through an achiral pathway was competitive with the catalyzed addition to form only one of the diastereomers.

21

The crystallographic coordinates of 7 have been deposited with the Cambridge Crystallographic Data Centre (CCDC); deposition no. 776146. These data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/data_request/cif.

22

For computational and mechanistic studies, see ref. 15g. For a full kinetic analysis, see ref. 19.