Catalytic intermolecular C(sp3)—H amination with sulfamates for the asymmetric synthesis of amines

This manuscript reports a practical catalytic asymmetric benzylic C(sp3)—H amination through the intermolecular insertion of a rhodium-bound nitrene species. The reaction of various substrates used as the limiting component, with a readily accessible sulfamate PfbsNH2 and the chiral rhodium(II) catalyst Rh2(S-tfptad)4 in the presence PhI(OPiv)2 can be performed on a multigram scale, affording the corresponding benzylic amines with high levels of efficiency and enantiocontrol. This process offers new opportunities for the asymmetric synthesis of amines.