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

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.