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. 2018 Nov 19;57(47):15430-15434.
doi: 10.1002/anie.201808598. Epub 2018 Oct 25.

Synthesis of Functionalized Cyclopropanes from Carboxylic Acids by a Radical Addition-Polar Cyclization Cascade

Chao Shu  1 , Riccardo S Mega  1 , Björn J Andreassen  1 , Adam Noble  1 , Varinder K Aggarwal  1
Affiliations

Synthesis of Functionalized Cyclopropanes from Carboxylic Acids by a Radical Addition-Polar Cyclization Cascade

Chao Shu et al. Angew Chem Int Ed Engl. .

Abstract

Herein, we describe the development of a photoredox-catalyzed decarboxylative radical addition-polar cyclization cascade approach to functionalized cyclopropanes. Reductive termination of radical-polar crossover reactions between aliphatic carboxylic acids and electron-deficient alkenes yielded carbanion intermediates that were intercepted in intramolecular alkylations with alkyl chlorides appended to the alkene substrate. The mild conditions, which make use of a readily available organic photocatalyst and visible light, were demonstrated to be amenable to a broad range of structurally complex carboxylic acids and a wide variety of chloroalkyl alkenes, demonstrating exquisite functional group tolerance.

Keywords: carboxylic acids; cyclopropanes; decarboxylation; photoredox catalysis; radical-polar crossover.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Photoredox‐catalyzed alkene difunctionalizations.
Scheme 2
Scheme 2
Optimized conditions.
Scheme 3
Scheme 3
Mechanistic studies.
Scheme 4
Scheme 4
Proposed mechanism.
See this image and copyright information in PMC

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