Remote chiral induction in the organocatalytic hydrosilylation of aromatic ketones and ketimines

ORGN 31

Andrei V. Malkov, amalkov@chem.gla.ac.uk1, Angus J. P. Stewart Liddon1, Pedro Ramirez-Lopez1, Lada Bendova1, David Haigh2, and Pavel Kocovsky, pavelk@chem.gla.ac.uk1. (1) Department of Chemistry, University of Glasgow, Glasgow, G12 8QQ, United Kingdom, (2) Medicines Research Centre, GlaxoSmithKline, Stevenage, United Kingdom
A new, practical, metal-free protocol has been developed for the enantioselective reduction of prochiral aromatic ketones (94% ee) and ketimines (87% ee). The method relies on trichlorosilane as the stoichiometric reducing agent that is activated by novel pyridine-type oxazolines as Lewis-basic organocatalysts. The reaction is characterized by an unusual, long-ranging chiral induction and is believed to be aided by arene-arene interactions between the catalyst and the substrate, as evidenced by quantum chemistry calculations.
 

Asymmetric Reactions and Syntheses
8:00 AM-11:40 AM, Sunday, 26 March 2006 Georgia World Congress Center -- C302, Oral

Division of Organic Chemistry

The 231st ACS National Meeting, Atlanta, GA, March 26-30, 2006