Mechanism and basis for enantioselectivity of the thiourea-catalyzed cyanosilylation of ketones

ORGN 20

Stephan J. Zuend, zuend@fas.harvard.edu and Eric N. Jacobsen, jacobsen@chemistry.harvard.edu. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St, Cambridge, MA 02138
We have investigated the mechanism of the enantioselective, thiourea-catalyzed addition of trimethylsilyl cyanide to ketones using both experimental and computational methods. Our results suggest a highly organized transition structure in which the catalyst activates both the nucleophile and the electrophile. We probe how the different components of the catalyst contribute to high enantioselectivity and reactivity, and we discuss the implications of our results on the development of new reactions.

 

Asymmetric Reactions and Syntheses
8:00 AM-12:20 PM, Sunday, 10 September 2006 Moscone Center -- Room 131, Oral

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006