Catalytic Decarbonylation of Aldehydes: Recent Advances and Future Perspectives

This review highlights the expanding role of decarbonylation in modern organic chemistry. Inspired by nature's enzymatic pathways, aldehyde decarbonylation, which enables C−C bond cleavage with the release of carbon monoxide, has emerged as a powerful and versatile transformation in sustainable synthesis, complex molecule modification, and late‐stage functionalization. Herein, we summarize recent advances (2021–2025) in both direct decarbonylation and decarbonylative functionalization of aldehydes, the two most significant classes of decarbonylation reactions. Special attention is given to cutting‐edge developments in transition‐metal catalysis, including Rh‐, Ir‐, Co‐, Ni‐, and Pd‐based systems, as well as photocatalytic and metal‐free protocols, which typically proceed through radical pathways and achieve high selectivity under mild conditions. By bridging classical catalytic methods with emerging radical‐driven approaches, this review underscores the growing impact of decarbonylative chemistry in green synthesis, pharmaceutical innovation, and biomass valorization.