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. 2013 Mar 6;135(9):3411-3.
doi: 10.1021/ja401182a. Epub 2013 Feb 19.

Catalytic enantioselective epoxidation of tertiary allylic and homoallylic alcohols

José Luis Olivares-Romero  1 , Zhi Li, Hisashi Yamamoto
Affiliations

Catalytic enantioselective epoxidation of tertiary allylic and homoallylic alcohols

José Luis Olivares-Romero et al. J Am Chem Soc. .

Abstract

An efficient and versatile method for the enantioselective epoxidation of both tertiary allylic and homoallylic alcohols catalyzed by Hf(IV)-bishydroxamic acid (BHA) complexes is described. Asymmetric epoxidation, kinetic resolution, and desymmetrization have been developed, demonstrating the flexible nature of the Hf(IV)-BHA system. This is the first report in which these substrates were obtained with enantioselectivities of up to 99%.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Chiral bishydroxamic acids.
Scheme 1
Scheme 1
Enantioselective Epoxidation of Tertiary Allylic Alcoholsa,b, aIsolated yields. bEnantiomeric excess values were determined by chiral HPLC or chiral gas chromatography.
Scheme 2
Scheme 2
Enantioselective Epoxidation of Tertiary Homoallylic Alcoholsa,b, aIsolated yields. bEnantiomeric excess values were determined by chiral HPLC or chiral gas chromatography. cEnantiomeric excess values were determined by 1H NMR in the presence of Eu(hfc)3.
See this image and copyright information in PMC

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