Remote 1,5-Difunctionalization of Alkenes via a Sulfinyl-Smiles Rearrangement and Vinylcyclopropane Ring-Opening Cascade.

The enantioselective remote difunctionalization of alkenes via radical pathways remains a major challenge due to limited stereocontrol in open-shell processes. We report a photoredox-catalyzed asymmetric remote 1,5-difunctionalization of alkenes that combines the strain-release ring opening of vinylcyclopropanes with a stereocontrolled sulfinyl-Smiles rearrangement. This multistep radical cascade bypasses kinetically disfavored hydrogen atom transfer pathways and enables precise site selectivity with excellent enantioselectivity. Both sulfur- and carbon-centered radicals are accommodated, providing efficient access to enantioenriched α-aryl γ,δ-unsaturated amides and derivatives thereof under mild conditions.