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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 which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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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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