Computational insights into the [Ni]H-catalyzed remote C(sp(3))-H hydroamidation of alkenes: mechanism and insertion selectivity

The mechanism and insertion selectivity of the [Ni]H-catalyzed C(sp(3))-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.