Computational insights into the [Ni]H-catalyzed remote C(sp3)–H hydroamidation of alkenes: mechanism and insertion selectivity

Abstract

The mechanism and insertion selectivity of the [Ni]H-catalyzed C(sp³)–H hydroamidation of 5-benzylthio-pentene have been investigated using density function theory calculations. A complete catalytic mechanism involving chain-walking, CO₂ extrusion, nitrene insertion, amido protonation and catalyst regeneration has been established. The origin of the nitrene group favorably inserting into the Ni–C bond over the C–H bond has been revealed for the first time.