A mild migratory reductive acyl cross-coupling has been achieved through NiH-catalyzed chainwalking and subsequent cross-coupling from two abundant starting materials, alkyl bromides, and carboxylic acids. This strategy allows the direct acylation of the benzylic sp3 C–H bond with high yield as a single regioisomer. As an alternative, the alkyl bromide could be replaced by the proposed olefin intermediate and commercially available n-PrBr to achieve a remote hydroacylation process.

Direct and positionally selective aliphatic C-H functionalization is an attractive means with which to streamline chemical synthesis. With many possible reaction sites, most traditional methods need a polar-directing group nearby to achieve high regioand chemoselectivity and are often restricted to a single site of functionalization. Here, we report a nondirected, remote sp 3 C-H amination process with predictable and switchable regioselectivity. This reaction uses a nickel hydride-catalyzed remote relay hydroamination strategy in which an aliphatic amino group is installed at a position far from the original C=C bond present in all unsaturated hydrocarbon substrates. Depending on the choice of ligand, either terminal or benzylic functionalization products can be obtained with excellent levels of regioselectivity.We also show that an alkyl bromide could also be used as an olefin precursor when using Mn 0 as a reductant. The utility of this transformation is further highlighted by the regioconvergent migratory hydroamination of isomeric mixtures of olefins forming single isomers of value-added benzylic or linear amines.

We report the hydrofluorination of unactivated alkenes using N-fluorobenzenesulfonimide as a fluorination reagent. The reaction produces exclusively Markovnikov hydrofluorination products under mild conditions. It is not affected by air or moisture and uses an inexpensive and readily available nickel compound as a catalyst. Distinct from the previously reported ionic pathway of the NiH-catalyzed hydrofunctionalization of olefins, this reaction was shown to proceed through a hydrogen atom transfer pathway.

We report a ligand-controlled nickel-catalyzed reductive hydroarylation of styrenes with predictable and controllable regioselectivity. With a diamine ligand, the reaction produces selective linear hydroarylation products. Alternatively, with a chiral PyrOx ligand. branch-selective enantio-enriched 1,1-diarylalkane products are obtained. Preliminary mechanistic results are consistent with a reductive Heck process.