Site- and stereoselective silver-catalyzed intramolecular amination of electron-deficient heterobenzylic C-H bonds.

We report a method for the site- and stereoselective intramolecular amination of electron-deficient heterobenzylic C-H bonds silver-catalyzed nitrene transfer (NT). A silver complex supported by a tripodal piperidine-based ligand afforded excellent reactivity under mild conditions (up to 96% yield), site-selectivity (up to >20 : 1), and diastereoselectivity (up to >20 : 1 dr) for the amination of heterobenzylic C-H bonds that reacted poorly with other metal-based catalysts for NT. Our catalyst proved highly amenable to substrates bearing diverse competing sites for functionalization, including complex molecules derived from pharmaceuticals and natural products.