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. 2015 Sep 23;137(37):11938-41.
doi: 10.1021/jacs.5b08304. Epub 2015 Sep 15.

Fragment Couplings via CO2 Extrusion-Recombination: Expansion of a Classic Bond-Forming Strategy via Metallaphotoredox

Chi Chip Le  1 , David W C MacMillan  1
Affiliations

Fragment Couplings via CO2 Extrusion-Recombination: Expansion of a Classic Bond-Forming Strategy via Metallaphotoredox

Chi Chip Le et al. J Am Chem Soc. .

Abstract

In this study we demonstrate that molecular fragments, which can be readily coupled via a simple, in situ RO-C═OR bond-forming reaction, can subsequently undergo metal insertion-decarboxylation-recombination to generate Csp(2)-Csp(3) bonds when subjected to metallaphotoredox catalysis. In this embodiment the conversion of a wide variety of mixed anhydrides (formed in situ from carboxylic acids and acyl chlorides) to fragment-coupled ketones is accomplished in good to high yield. A three-step synthesis of the medicinal agent edivoxetine is also described using this new decarboxylation-recombination protocol.

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Figures

Scheme 1
Scheme 1
Mechanism of CO2 Extrusion–Recombination
See this image and copyright information in PMC

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