Natural product syntheses carbonylative cyclizations

Covering: 2000-2018 In this review, we highlight recent examples of natural product total syntheses employing transition metal-mediated/catalyzed carbonylative cyclization strategies to build key ring systems. It mainly covers carbonylative cyclizations for the construction of O-heterocycles, N-heterocycles and carbocycles including cyclic ketones and phenols. The reaction types include carbonylation of epoxide to β-lactones, carbonylative (macro)lactonization/lactamization, the Semmelhack reaction, tandem hydroformylation-cyclization, the Pauson-Khand reaction, carbonylative C-H activation cyclization, the Stille/Suzuki carbonylation, [ n + m + 1] carbonylative cycloaddition, the Dötz annulation, and others. This review summarizes the application of various transition metal-catalyzed/mediated carbonylative cyclization reactions in natural product total synthesis.