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

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 Csp2–Csp3 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.