Metal-Catalyzed C–H Bond Oxidation in the Total Synthesis of Natural and Unnatural Products

Abstract C–H bond oxidation is a powerful means for oxygen incorporation in organic molecules. Its use results in fast structural diversification and in a new way of thinking about retrosynthetic disconnections. In this review, we present the application of five metal-catalyzed methodologies for C(sp 3)–H oxidation in the total synthesis of natural and unnatural products, covering the period of 2004–2022. 1 Introduction 2 Copper-Mediated Hydroxylation of Methylenes β to Imines 3 Palladium Acetoxylation of Methyl Groups β to Oximes 4 Palladium-Mediated Allylic C–H Bond Oxidation of Terminal Olefins 5 Iron- and Manganese-Mediated Aliphatic Oxidation 6 Miscellaneous 7 Conclusion