Application of Transition Metal‐Catalyzed Decarbonylation of Aldehydes in the Total Synthesis of Natural Products

Abstract Decarbonylation is an invaluable reaction, utilized by nature and chemists alike. In different life forms, such as prokaryotes, plants and animals, this transformation is catalyzed by aldehyde decarbonylases. In the laboratory, the transition metal‐catalyzed (TMC) decarbonylation, which was first achieved in 1959, is by and large the dominant way for conducting this reaction. The carbon‐carbon bond cleavage is most often made possible by RhCl(PPh 3 ) 3 i. e. Wilkinson's catalyst, but other metals are also used, both in academia and in industry. In this review, we chose to present the applications of TMC decarbonylation in the synthesis of natural products and their derivatives. More than 30 examples are showcased and categorized into three categories based on the essence of the role of the aldehyde group in the synthesis. A short outlook is given in the end, listing the different advantages and disadvantages of Wilkinson's catalyst, as well as offering a brief prospect for the future.