Angewandte Chemie 03.24

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

Yawen Hu, Cédric Hervieu,  Dr. Estíbaliz Merino*, Prof. Cristina Nevado*

Angew. Chem. Int. Ed. 2024, Early View
DOI: anie.202319158

An efficient asymmetric remote arylation of C(sp3)−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.