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

Abstract

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 α,β-Unsaturated Aldehydes

5 Aerobic Enantioselective Synthesis of Dihydropyranones

6 Conclusion

Keywords

NHC - aerobic oxidation - oxygen - biomimetic synthesis - ­organocatalysis - green chemistry - asymmetric synthesis

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