Cobalt-Catalyzed Highly Regioselective Alkoxycarbonylation of Olefins Driven by Light

Alkoxycarbonylation of olefins is a pivotal transformation in the production of esters; however, attaining high regioselectivity in this transformation, specifically using industrially relevant aliphatic olefins, remains a formidable challenge. To date, this objective has been achieved exclusively through the integration of precious Pd catalysts and costly phosphine ligands in a pressurized CO environment at high temperatures. In this study, we present a novel cobalt-catalyzed light-driven protocol for achieving excellent regioselectivity under mild conditions. Specifically, we demonstrate the efficacy of converting propylene, as well as terminal and internal linear olefins, to the corresponding terminal esters with over 90% regioselectivity, accompanied by a wide range of alcohols. Control experiments and DFT computations reveal that light promotes the formation and maintains the concentration of the key species HCo(CO)₃.