Recent advances in nickel-catalyzed reductive hydroalkylation and hydroarylation of electronically unbiased alkenes

Tremendous advances have been made in nickel catalysis over the past decade. Several key properties of nickel, such as facile oxidative addition and ready access to multiple oxidation states, have allowed the development of a broad range of innovative reactions. In recent years, these properties have been increasingly understood and used to perform transformations long considered exceptionally challenging. Here we discuss some of the most recent and significant developments in homogeneous nickel catalysis, with an emphasis on both synthetic outcome and mechanism.

Cofactor-mimetic aerobic oxidation has conceptually merged with catalysis of syngas reactions to form a wide range of Markovnikov-selective olefin radical hydrofunctionalizations. We cover the development of the field and review contributions to reaction invention, mechanism, and application to complex molecule synthesis. We also provide a mechanistic framework for understanding this compendium of radical reactions.