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(PPh3)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.

Decarbonylation of benzaldehydes by dual photoorgano-cobalt catalysis

“…1 In the laboratory, however, the main strategies in the chemist's repertoire depend on the combination of noble-metal catalysts and high temperatures, wherein C–H insertion of the metal into the aldehyde bond plays a key role (Scheme 1a). 2 In the last years, progress has been made within the field of photochemistry to offer milder and more sustainable alternatives. Simultaneously, there is growing interest for new methodologies designed to defunctionalize and process biologically derived materials, reducing its oxygen content by cleaving syngas (CO + H 2 ) for instance.…”

Regioselective Aldehyde Decarbonylation through Palladium-Catalyzed Nitrile Boronic Acid Cross-Coupling

“…Regardless of these numerous methods for aldehyde decarbonylation, none are capable of differentiating various aldehydes and indiscriminately remove CO from all formyl groups, often requiring chemists to mask desired aldehydes in different oxidation states, lengthening synthetic routes. 16…”

Effects of phosphine ligands in nickel-catalyzed decarbonylation reactions of lactone

“…Transition-metal-catalyzed decarbonylation has become a hot topic since 2010, because it provides a novel and creative synthetic strategy using carbonyl groups as "traceless handles". [4][5][6][7] For several years, chemists have been researching the utilization of various transition-metal catalysts, such as ruthenium, [8][9][10][11][12][13][14] palladium, [15][16][17][18][19] rhodium, [20][21][22][23] and nickel, [24][25][26][27][28] to facilitate decarbonylation reactions. These approaches have demonstrated significant success in the field of chemistry.…”