A carbamoyl fluoride-enabled enantioselective Ni-catalyzed carbocarbamoylation of unactivated alkenes was developed, providing a broad range of chiral γ-lactams bearing an all-carbon quaternary center in 45−96% yield and 38−97% ee.

Enantioselective Ni-catalyzed C(sp 3 )À H bond activation remains an elusive challenge. Herein, we used phosphine oxide-ligated NiÀ Al bimetallic catalyst to realize enantioselective Ni-catalyzed aliphatic C(sp 3 )À H activation of formamides, providing a series of chiral Ncontaining heterocycles in 40-95 % yield and 70-95 % ee.

A bifunctional secondary phosphine oxide (SPO) ligand-controlled method was developed for Ni−Al-catalyzed nonchelated dual C−H annulation of arylformamides with alkynes, providing a series of substituted amide-containing heterocycles in ≤97% yield. The SPO-bound bimetallic catalysis proved to be critical to the reaction efficiency.

Compared with the widely explored exo-selective C–H cyclization, transition metal-catalyzed endo-selective C–H cyclization of benzimidazoles with alkenes has been a formidable challenge. Previous efforts mainly rely on substrate-controlled methods, rendering the product complexity restricted. Herein we report a catalyst-controlled method to facilitate endo-cyclization, in which a bulky N-heterocyclic carbene ligand and t BuOK base-enabled Ni–Al bimetallic catalyst prove critical to the endo selectivity.

Enantioselective Ni-catalyzed C(sp 3 )À H bond activation remains an elusive challenge. Herein, we used phosphine oxide-ligated NiÀ Al bimetallic catalyst to realize enantioselective Ni-catalyzed aliphatic C(sp 3 )À H activation of formamides, providing a series of chiral Ncontaining heterocycles in 40-95 % yield and 70-95 % ee.