Computational Insights into the Reaction Mechanisms of Nickel-Catalyzed Hydrofunctionalizations and Nickel-Dependent Enzymes

Abstract

For several decades, transition-metal catalysis has been a popular method for many functional group transformations in organic chemistry. Recent developments in sustainability and applications of earth-abundant metals have resulted in a synthetic renaissance and have attracted considerable interest in less toxic and inexpensive first-row transition-metal catalysts such as nickel. Herein, we highlight some recent computational insights into the reaction mechanisms of Ni-catalyzed hydrofunctionalizations (i.e., hydrogenation, hydrovinylation, hydroacylation, hydroheteroarylation, hydrosilylation, and hydroalkoxylation) and Ni-dependent enzymes (i.e., lactate racemase, methyl-CoM reductase, and [NiFe]-hydrogenase). These computational studies provide insights into these reaction mechanisms and thus assist in the development and design of sustainable catalysts.