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Molecules 2012, 17(2), 1617-1634; doi:10.3390/molecules17021617
Article

Enantioselective Synthesis of 2,2-Disubstituted Terminal Epoxides via Catalytic Asymmetric Corey-Chaykovsky Epoxidation of Ketones

1
,
1
,
1,*  and 2,*
1 Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan 2 Institute of Microbial Chemistry, Tokyo, Kamiosaki 3-14-23, Shinagawa-ku, Tokyo 141-0021, Japan
* Authors to whom correspondence should be addressed.
Received: 16 December 2011 / Revised: 23 January 2012 / Accepted: 31 January 2012 / Published: 7 February 2012
(This article belongs to the Special Issue Asymmetric Catalysis)
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Abstract

Catalytic asymmetric Corey-Chaykovsky epoxidation of various ketones with dimethyloxosulfonium methylide using a heterobimetallic La-Li3-BINOL complex (LLB) is described. The reaction proceeded smoothly at room temperature in the presence of achiral phosphine oxide additives, and 2,2-disubstituted terminal epoxides were obtained in high enantioselectivity (97%–91% ee) and yield ( > 99%–88%) from a broad range of methyl ketones with 1–5 mol% catalyst loading. Enantioselectivity was strongly dependent on the steric hindrance, and other ketones, such as ethyl ketones and propyl ketones resulted in slightly lower enantioselectivity (88%–67% ee).
Keywords: asymmetric catalysis; asymmetric synthesis; epoxide; rare earth metal; sulfur ylide asymmetric catalysis; asymmetric synthesis; epoxide; rare earth metal; sulfur ylide
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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Sone, T.; Yamaguchi, A.; Matsunaga, S.; Shibasaki, M. Enantioselective Synthesis of 2,2-Disubstituted Terminal Epoxides via Catalytic Asymmetric Corey-Chaykovsky Epoxidation of Ketones. Molecules 2012, 17, 1617-1634.

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