Radical Amination of C(sp3)?H Bonds Using N?Hydroxyphthalimide and Dialkyl Azodicarboxylate

摘要

A direct conversion of C(sp3)−H bonds tonC(sp3)−N bonds has been achieved by utilizing catalytic Nhydroxyphthalimiden(NHPI) and stoichiometric dialkylnazodicarboxylate. NHPI functions as a precursor of thenelectron-deficient phthalimide N-oxyl radical (PINO) tonabstract hydrogens, and dialkyl azodicarboxylate acts as antrapping agent of the resultant carbon radical to generate thenhydrazine derivatives. This C−H amination proceeds in anhighly chemoselective manner with a wide applicability to functionalize benzylic, propargylic, and aliphatic C−H bonds.nFurthermore, the obtained hydrazine compounds were readily converted to the corresponding carbamates or amines. Hence, thenpresent protocol for direct introduction of the nitrogen functionality serves as a powerful tool for efficient construction ofnnitrogen-substituted natural products and pharmaceuticals.