Photoexcited Direct Amination/Amidation of Inert Csp3–H Bonds via Tungsten–Nickel Catalytic Relay

Light alkanes are the most abundant resources in nature. It is of great significance to develop convenient methods to realize the conversion of alkanes to high value-added products. However, the examples of aliphatic amines derived from unactivated alkanes remain rare. This work describes a rapid construction of C(sp3)–N bonds from light alkanes with amine/amide electrophile reagents via high-valent tungsten and nickel catalysis in high efficiency. The photoexcited metal relay provides a powerful tool for the activation of inert sp3-hybridized C–H bonds and stabilization of C–Ni(III)–N intermediates.