Abstract

AbstractUnactivated 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.

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