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. 2011 Jun 8;133(22):8432-5.
doi: 10.1021/ja201873d. Epub 2011 May 16.

Iron-catalyzed asymmetric epoxidation of β,β-disubstituted enones

Yasuhiro Nishikawa  1 , Hisashi Yamamoto
Affiliations

Iron-catalyzed asymmetric epoxidation of β,β-disubstituted enones

Yasuhiro Nishikawa et al. J Am Chem Soc. .

Abstract

The combination of Fe(OTf)(2) and novel phenanthroline ligands enables the catalytic asymmetric epoxidation of acyclic β,β-disubstituted enones, which have been a heretofore inaccessible substrate class. The reaction provides highly enantioenriched α,β-epoxyketones (up to 92% ee) that can be further converted to functionalized β-ketoaldehydes with an all-carbon quaternary center.

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Figures

Figure 1
Figure 1
X-ray structure of [Fe(L3)2(CH3CN)(OTf)](OTf) is shown as CPK model. Thermal ellipsoids correspond to 50 % probability. Hydrogen atoms and non-coordinating molecules are omitted for clarity. Triflate group and CH3CN are replaced by a green atom and a yellow atoms for clarity, respectively. See supporting information for details. C: gray, N: blue, Fe: red.
Scheme 1
Scheme 1
The epoxidation of acyclic β,β-disubstituted carbonyl compounds.
Scheme 2
Scheme 2
The asymmetric epoxidation with a non-activated olefin and a competitive experiment using electron-rich and electron-deficient olefins.
Scheme 3
Scheme 3
The transformations of optically active α,β-epoxyketones.
See this image and copyright information in PMC

References

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    1. For reviews on iron catalysis, see: Enthaler S, Junge K, Beller M. Angew Chem Int Ed. 2008;47:3317.Bolm C, Legros J, Le Paih J, Zani L. Chem Rev. 2004;104:6217.

    1. For the seminal work on non-heme iron-catalyzed epoxidation: White MC, Doyle AG, Jacobsen EN. J Am Chem Soc. 2001;123:7194.

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