Abstract

Nickel catalysis offers exciting opportunities for organic synthesis. However, our mechanistic understanding, and our appreciation of catalyst and substrate structure/reactivity relationships has not kept up with the breakneck pace of synthetic innovations. Our research programme is developing a quantitative and systematic understanding of fundamental processes in nickel catalysis. We use a range of techniques from organometallic synthesis, organic synthesis, physical organic chemistry, and computational chemistry to probe these processes, with a focus on oxidative addition. Our work so far has: identified the role of halide abstraction in the reactions of Ni⁰ complexes with aryl halides, and how this depends on ligand and substrate structure; developed an understanding of oxidative addition to Ni⁰ complexes with bidentate phosphine ligands such as dppf; identified functional groups that lead to privileged substrates or catalyst inhibitors that can completely shut down cross-coupling reactions; and developed an understanding of the mechanisms of the reactions of alkyl halides with Ni⁰. This presentation will cover recent research topics, particularly the reactions of alkyl halides with Ni⁰, and how an understanding of fundamental reactivity can be used to design more efficient cross-coupling reactions.