Recent Advances in Ni-Catalyzed 1,1-Difunctionalization of Unactivated Olefins

Unactivated olefins rank amongst the most important feedstocks in organic synthesis. Their availability makes them particularly useful synthons for subsequent functionalization, particularly in a catalytic manner. Driven by the popularity ascribed by nickel catalysis as a new tool to rapidly forge molecular architectures via one-or two-electron manifolds, the recent years have witnessed significant advances in Ni-catalyzed olefin difunctionalization. While 1,2-difunctionalization or remote functionalization via “chain-walk” have become mature disciplines for repurposing the potential of olefins as building blocks, it was only recently that extensions of this chemistry to 1,1-difunctionalization have been possible. This review summarizes the recent advances in Ni-catalyzed olefin 1,1-difunctionalization, holding considerable promise as a new powerful strategy for our ever-growing synthetic repertoire.