Iridium-Catalyzed, Regio- and Stereoselective Silylation of Primary and Secondary C( <i>sp</i> ³ )–H Bonds in Primary Amines

The functionalization of amines at C-H bonds beyond the α-position could generate valuable difunctional products, but such transformations with readily accessible amine derivatives remain underdeveloped. We report the iridium-catalyzed, regio- and stereoselective silylation of primary and secondary C(sp³)-H bonds in primary amine derivatives to afford silapyrrolidines and 1,2-amino alcohols after oxidation. The use of sulfonamides as protecting groups on the alkyl amines enables alkylation of the resulting sulfonamide with halomethylsilanes and subsequent silylation of the C(sp³)-H bonds with broad scope. This reaction also enables the functionalization of both primary and secondary C(sp³)-H bonds with high regioselectivity and stereoselectivity. Reactions with iridium complexes of new chiral nitrogen-based ligands occur with high enantioselectivity.