Nickel-Catalyzed Reductive Decarboxylative Coupling of Diacyl Peroxides with Aryl/Vinyl Halides

Abstract

In this work, we utilized alkyl diacyl peroxides as the decarboxylative substrates, which are derived from the condensation of readily available alkyl acids with mCPBA, to couple with a variety of aryl and vinyl halides under a Ni-catalyzed cross-electrophile coupling platform, effectively affording C(sp³)–C(sp²) bonds. The method stresses the high compatibility of alkyl diacyl peroxides as strong oxidants with the Ni/Zn-mediated reductive conditions. With assistance of LiI and catalytic CuI, the kinetic labile alkyl diacyl peroxide underwent facile in situ Barton-decarboxylative iodination to afford alkyl iodide as the actual coupling partners. The present method showcases a broad substrate scope for both alkyl acids and aryl/vinyl electrophiles. It offers the advantage of iodo-selectivity for the alkylation of aryl iodides, even those bearing highly competing bromine groups, including the challenging vicinal bromoiodobenzene. Consequently, it enables the development of a one-pot selective dialkylation process.