Photoredox-Catalyzed Alkene Acylesterification with Acyloxime Esters via C-C and Tertiary C-O Bond Formation

We describe an efficient acyl esterification method for alkenes utilizing acyloxime esters as bifunctional reagents featuring radical acylation and congested C-O bond formation. This approach is characterized by mild photoredox conditions, high step and atom economy, a broad substrate scope, and excellent regioselectivity. A variety of valuable α-acyl hindered alcohol esters, including those obtained via gram-scale synthesis and late-stage functionalization of pharmaceutical molecules, were presented, demonstrating its synthetic potential and practicability.