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. 2013 Nov 25;52(48):12655-8.
doi: 10.1002/anie.201307790. Epub 2013 Oct 16.

Enantioselective functionalization of radical intermediates in redox catalysis: copper-catalyzed asymmetric oxytrifluoromethylation of alkenes

Rong Zhu  1 , Stephen L Buchwald
Affiliations

Enantioselective functionalization of radical intermediates in redox catalysis: copper-catalyzed asymmetric oxytrifluoromethylation of alkenes

Rong Zhu et al. Angew Chem Int Ed Engl. .

Abstract

A method for the efficient enantioselective oxytrifluoromethylation of alkenes has been developed using a copper catalyst system. Mechanistic studies are consistent with a metal-catalyzed redox radical addition mechanism, in which a C–O bond is formed via the copper-mediated enantioselective trapping of a prochiral alkyl radical intermediate derived from the initial trifluoromethyl radical addition.

Keywords: asymmetric catalysis; copper; enantioselectivity; radicals; synthetic methods.

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Figures

Scheme 1
Scheme 1
Background of the methodology development.
Scheme 2
Scheme 2
(a) Radical clock experiments. (b) TEMPO trapping experiment.
Scheme 3
Scheme 3
(a) Trisubstituted alkenes as mechanistic probes.[a] (b) Rationale for the product distribution observed.
Scheme 4
Scheme 4
Mechanistic proposal.
See this image and copyright information in PMC

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