Oxone-Mediated Radical Trifunctionalization of Allyl Carboxylates via 1,2-Ester Migration

Radical-mediated trifunctionalization of alkenes, by enabling the rapid introduction of multiple functional groups, has emerged as one of the most effective strategies for the construction of functionally diverse and structurally complex molecules. Herein, we present a novel potassium peroxomonosulfate (Oxone)-mediated 1,2-ester migration strategy for the radical trifunctionalization of allyl carboxylates. This is the first case of achieving 1,3-hydroxyselenation or 1,3-hydroxysulfurization of allyl carboxylates via 1,2-ester migration, and Oxone served as both the oxidant and the hydroxyl source. The reaction efficiently constructs a C-Se/S bond and two C-O bonds in one step. Furthermore, combined experimental and density functional theory (DFT) calculations elucidate the reaction mechanism, revealing that the 1,2-ester migration can be realized through dual pathways, the three-membered (with an activation energy of 13.7 kcal/mol) and five-membered (with an activation energy of 14.6 kcal/mol) ring transition states.