Pd‐Catalyzed Aerobic Oxidation Reactions: Industrial Applications and New Developments

This chapter survey a number of other Palladium (Pd)-catalyzed oxidation reactions that have industrial significance, including acetoxylation of ethylene to vinyl acetate, oxidative carbonylation of alcohols to dialkyl oxalates and carbonates, and oxidative coupling of dimethyl phthalate to 3,3',4,4'-tetramethyl biphenylcarboxy-late. It highlights other reactions of potential industrial significance, including the oxidation of alcohols to aldehydes and ketones, oxida-tive coupling of arenes and carboxylic acids to afford aryl esters, benzylic acetoxylation, and oxidative Heck reactions. There are several serious challenges associated with Pd-catalyzed aerobic oxidations. These include controlling the chemo- and regioselectivity, promoting the oxidizing ability of PdII, particularly in challenging oxidation reactions, and enhancing the Pd catalyst lifetime. The chapter describes a few new developments in Pd oxidation catalysis that point toward potential solutions to the aforementioned challenges. The key to success in Pd oxidation reactions is the ability to achieve efficient aerobic catalytic turnover, minimize catalyst deactivation, and control the reaction selectivity.