Mechanism of palladium-catalyzed allylic substitution of tertiary allylic carbonates with sodium sulfinates: unusual bifunctional nucleophile-enabled inner-sphere pathway and origin of regio- and enantioselectivities

DFT calculations were performed to investigate Pd-catalyzed allylic sulfonylation of tertiary allylic carbonates. The bifunctional role of the sulfonate nucleophile enables the C–S bond formation via a unique inner-sphere pathway.