Palladium‐Catalyzed Transfer Hydrocarbonylation of Alkenes and Alkynes with Formic Acid Derivatives

Transition‐metal‐catalyzed hydrocarbonylation constitutes a fundamental method for constructing carbonyl‐containing compounds with 100% atom economy. Despite its industrial relevance, the traditional hydrocarbonylation reaction employing pressurized CO has limited applicability in laboratory‐scale synthesis. To address this limitation, transfer hydrocarbonylation has emerged as a distinct alternative. This approach has circumvented the need for both external gaseous CO and separate nucleophiles by employing integrated transfer reagents that supply all requisite components. As a result, it has achieved high atom economy while offering enhanced operational simplicity under mild conditions. This review provides a systematic overview of palladium‐catalyzed transfer hydrocarbonylation of alkenes and alkynes. The discussion encompasses transfer hydroesterification, hydroaminocarbonylation, hydrothiocarbonylation, and hydrocarboxylation, with a particular focus on substrate scope, regioselectivities, and mechanistic insights. By integrating these developments, we provide a forward‐looking perspective on the role of this method in advancing valuable and practical synthesis of carbonyl compounds.