Nickel‐Catalyzed Carbonylations

Abstract

Carbonylation reactions using carbon monoxide as one of the inexpensive C1 sources have gained much attention. They are the direct and easy choices for the synthesis of several carbonyl-containing compounds while some of those procedures have been industrialized. However, studies on the transition-metal-catalyzed carbonylation reaction were more focused on the use of noble metal catalysts. Although these catalytic systems were advantageous in terms of reactivity and efficiency, their high costs and toxicity are the biggest concern for several potential applications. Hence, the advancement of similar effective catalysts is in urgent need. Nickel may serve as an easy alternative as the first-row transition metal similar to palladium. However, the accidental occurrence and stability of toxic Ni(CO) 4 in the presence of CO has sometimes limited the applications of nickel-based catalysis. Nevertheless, controlled release of CO from CO surrogates for the stability of nickel catalysts has helped to solve the problem recently. In the past 10 years, the Ni-catalyzed carbonylation reaction has been successfully evolved as a promising methodology for the synthesis of various molecules such as alkyl ketones, benzophenones, α,β-alkynyl ketones, aryl amides, α,β-unsaturated carboxylic acids, iodoester derivatives, γ-lactams, and even few biologically active molecules. Moreover, apart from monocarbonylation, double carbonylation also has been achieved by tuning the reaction conditions. The nickel-catalyzed [2+2+1] carbonylative cycloaddition reaction between norbornenes and allyl halides, carbonylative Negishi cross-coupling reaction, carbonylative Sonogashira reaction, carbonylative fluoroalkylation reaction, and carbonylative alkenyl–aryl, alkenyl–alkenyl, and alkenyl–alkyl coupling reactions and use of CO surrogates or atmospheric pressure of CO at room temperature conditions are important examples in the literature of carbonylation reactions. This chapter covers the reaction methodology of Ni-catalyzed carbonylation reaction mentioning the tuning of reaction conditions and substrate scopes and will highlight the main achievements of non-noble metal-catalyzed carbonylative transformations.