Highly chemoselective homologative assembly of the α-substituted methylsulfinamide motif from N-sulfinylamines.

α-Substituted methylsulfinamide are prepared through the homologation of electrophilic N-sulfinylamines with Li-CHXY reagents. The transformation takes place under full chemocontrol and exhibits good flexibility for preparing both N-aryl and N-alkyl analogues. Various sensitive functionalities can be accommodated on the starting materials, thus documenting a wide reaction scope.