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. 2016 Apr 13;138(14):4722-5.
doi: 10.1021/jacs.6b01728. Epub 2016 Mar 29.

Enantioselective Photocatalytic [3 + 2] Cycloadditions of Aryl Cyclopropyl Ketones

Adrian G Amador  1 , Evan M Sherbrook  1 , Tehshik P Yoon  1
Affiliations

Enantioselective Photocatalytic [3 + 2] Cycloadditions of Aryl Cyclopropyl Ketones

Adrian G Amador et al. J Am Chem Soc. .

Abstract

Control of stereochemistry in photocycloaddition reactions remains a substantial challenge; almost all successful catalytic examples to date have involved [2 + 2] photocycloadditions of enones. We report a method for the asymmetric [3 + 2] photocycloaddition of aryl cyclopropyl ketones that enables the enantiocontrolled construction of densely substituted cyclopentane structures not synthetically accessible using other catalytic methods. These results show that the dual-catalyst strategy developed in our laboratory broadens synthetic chemists' access to classes of photochemical cycloadditions that have not previously been feasible in enantioselective form.

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Figures

Scheme 1
Scheme 1. Precedent and project objectives
Scheme 2
Scheme 2. Proposed mechanism for enantioselective [3+2] cycloaddition
Scheme 3
Scheme 3. Cleavage of the aryl ketone moiety
See this image and copyright information in PMC

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