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 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.
Merck Center for Catalysis at Princeton University , Princeton, New Jersey 08544, United States.
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Merck Center for Catalysis at Princeton University , Princeton, New Jersey 08544, United States.
David W C
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MacMillan
D000812:Anhydrides / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D028561:Transition Elements / Q000737:chemistry*
D000812:Anhydrides; D002264:Carboxylic Acids; D002712:Chlorides; D007659:Ketones; D028561:Transition Elements