Palladium-Catalyzed Intermolecular Carbonylation-Based Difunctionalization of Alkenes

Abstract The palladium(II)-catalyzed carbonylation of alkenes presents one of most efficient methods for the synthesis of alkyl-substituted carbonyls and has received much attention. In this Account, we summarize our recent studies on the palladium-catalyzed intermolecular carbonylation-based 1,2-difunctionalization of alkenes, in which two strategies were involved: (1) a cooperative strategy involves the sequential iodine(III)-mediated alkene activation and palladium-catalyzed carbonylation, leading to the intermolecular β-oxy-, fluoro-, and azidocarbonylation of alkenes; (2) the classic strategy initiated by intermolecular nucleopalladation and carbonylation, including the asymmetric oxycarbonylation of alkenes. These methods provide a series of efficient approaches to synthesize β-functionalized aliphatic carboxylic derivatives. 1 Introduction 2 A Cooperative Strategy Involving Iodine(III)-Mediated Alkene Activation and Palladium-Catalyzed Carbonylation 2.1 Intermolecular Oxycarbonylation of Alkenes 2.2 Intermolecular Fluorocarbonylation of Alkenes 2.3 Intermolecular Azidocarbonylation of Alkenes 3 Intermolecular Aminocarbonylation of Alkenes Initiated by Aminopalladation 4 Intermolecular Arylcarbonylation of Alkenes Initiated by Arylpalladation 5 Intermolecular Enantioselective Oxycarbonylation of Alkenes Initiated by Oxypalladation 6 Conclusion