Biomimetic Oxidative Carbene Catalysis: Enabling Aerial Oxygen as a Terminal Oxidant

Oxidative carbene catalysis is a quickly growing field in organic synthesis. However, these catalytic protocols traditionally rely on the stoichiometric addition of a high-molecular-weight oxidant, providing these reactions with a high E-factor. Here, we review efforts to replace high-molecular-weight oxidants with oxygen using a biomimetic system of coupled electron-transfer mediators. Two reactions are discussed: the aerobic oxidative esterification of aldehydes and the aerobic oxidative NHC-catalyzed enantioselective formation of dihydropyranones. 1 Introduction 2 Biomimetic Oxidations 3 Oxidative NHC Catalysis 4 NHC-Catalyzed Aerobic Oxidative Esterification of alpha,beta-Unsaturated Aldehydes 5 Aerobic Enantioselective Synthesis of Dihydropyranones 6 Conclusion