Catalytic Intermolecular C(Sp(3))-H Amination With Sulfamates For The Asymmetric Synthesis Of Amines

A practical catalytic asymmetric benzylic C(sp(3))-H amination through the intermolecular insertion of a rhodium-bound nitrene species is reported. The reaction of various substrates (used as the limiting component) with the readily accessible sulfamate PfbsNH(2) and the chiral rhodium(II) catalyst Rh-2 (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.