J. Am. Chem. Soc., 126 (27), 8352 -8353, 2004. 10.1021/ja049135l S0002-7863(04)09135-8
Web Release Date: June 18, 2004

Copyright © 2004 American Chemical Society

Asymmetric 1,4-Hydrosilylations of ,-Unsaturated Esters

Bruce H. Lipshutz,* Jeff M. Servesko, and Benjamin R. Taft

Department of Chemistry & Biochemistry, University of California, Santa Barbara, California 93106

lipshutz@chem.ucsb.edu

Received February 17, 2004

Abstract:

Complexing catalytic amounts of CuH with a nonracemic JOSIPHOS or SEGPHOS ligand, together with stoichiometric PMHS, leads to exceedingly efficient and highly enantioselective 1,4-reductions of ,-disubstituted enoates and lactones. An unprecedented substrate-to-ligand ratio of 7700:1 for this type of reaction is documented.


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