Facile Amine Formation by Intermolecular Catalytic Amidation of Carbon−Hydrogen Bonds

A simple copper-based catalytic system has been developed for the carbon−hydrogen amidation reaction. The copper−homoscorpionate complex TpBr3Cu(NCMe) catalyzes the transfer of the nitrene unit NTs (Ts = p-toluenesulfonyl) and its subsequent insertion into the sp3 C−H bonds of alkyl aromatic and cyclic ethers or the sp2 C−H bonds of benzene using PhINTs as the nitrene source, affording the corresponding trisubstitued NR1HTs amines in moderate to high yields. The use of the environmentally friendly chloramine-T has also proven effective, with the advantage that sodium chloride is formed as the only byproduct. A tandem, one-pot consecutive nitrene−carbene insertion system has been developed to yield amino acid derivatives.