Markovnikov Hydrocarbonylation of Unactivated Alkenes via Cobalt/Photoredox Dual Catalysis

Hydrocarbonylation of alkenes is one of the most fundamental transformations for the synthesis of carbonyl compounds. However, achieving Markovnikov-selective hydrocarbonylation of unactivated alkenes to afford branched products remains a challenge in conventional two-electron catalytic systems. Herein, we report a Markovnikov hydroalkoxycarbonylation of unactivated alkenes through cobalt-hydride and photoredox dual catalysis. This protocol exhibits a broad substrate scope, efficiently transforming mono-, di-, tri-, and even tetrasubstituted alkenes into branched esters bearing diverse functional groups. In addition, the versatility of this dual catalysis is demonstrated by Markovnikov hydroxycarbonylation of unactivated alkenes using water as the nucleophile to afford branched carboxylic acids. Mechanistic investigations support the cobalt-hydride species initiating the radical hydrocarbonylation via a CO-mediated hydrogen atom transfer (HAT), while the photoredox catalyst serves to shuttle the electron transfer of the cobalt intermediates.