Cobalt-Catalyzed Markovnikov-Selective Radical Hydroacylation of Unactivated Alkenes with Acylphosphonates

Acylphosphonates having the 5,5-dimethyl-1,3,2-dioxophosphinanyl skeleton are developed as efficient intermolecular radical acylation reagents, which enable the cobalt-catalyzed Markovnikov hydroacylation of unactivated alkenes at room temperature under mild conditions. The protocol exhibits broad substrate scope and wide functional group compatibility, providing branched ketones in satisfactory yields. A mechanism involving the Co–H mediated hydrogen atom transfer and subsequent trapping of alkyl radicals by acylphosphonates is proposed.