Asymmetric, Remote C(sp³)−H Arylation via Sulfinyl‐Smiles Rearrangement

An efficient asymmetric remote arylation of C(sp 3 )−H bonds under photoredox conditions is described here. The reaction features the addition radicals to a double bond followed by a site‐selective radical translocation (1, n ‐hydrogen atom transfer) as well as a stereocontrolled aryl migration via sulfinyl‐Smiles rearrangement furnishing a wide range of chiral α ‐arylated amides with up to >99 : 1 er. Mechanistic studies indicate that the sulfinamide group governs the stereochemistry of the product with the aryl migration being the rate determining step preceded by a kinetically favored 1, n ‐HAT process.