Palladium-Catalyzed Carbonylative Oxidation of Arenes, Alkanes, and Other Hydrocarbons

Abstract

Pd-catalyzed carbonylation of aryl, vinyl, and benzyl halides and pseudo aryl or vinyl halides is described. The authors give special focus to the intermolecular acylpalladation of π-bond systems and its related chemistry. Several unique features associated with the reactions of acylpalladium derivatives derivable from allyl-, propargyl-, and allenylpalladiums that are similar to those derivable from alkyl-, aryl-, alkenyl-, and alkynylpalladiums are discussed. The authors outline and discuss the three cyclic acylpalladation reactions: Types I-III Ac–Pd processes, polymeric acylpalladation, and direct noncarbonylative carbopalladation. Various specific examples follow. An extensive discussion of acylpalladation and cycocarbonylation is also included. Pd-catalyzed decarbonylation of acyl halides and aldehydes is summarized and a discussion on the interesting field of acylpalladium is included. The total syntheses of natural products using Pd-catalyzed carbonylation is described. The authors discuss the Pd-catalyzed carbonylative oxidation (oxidative carbonylation) reaction, especially the reaction of carbon monoxide and oxygen- or nitrogen-based nucleophiles. Industrial production of dialkyl oxalates, dialkyl carbonates, and related processes developed by Ube Industries is featured. The chapter concludes with a discussion of the synthesis of oligomers and polymers via migratory insertion of isonitriles as a prototypical example of other migratory insertion reactions.