Recent Strategies in Non-Heme-Type Metal Complex-Catalyzed Site-, Chemo-, and Enantioselective C–H Oxygenations

Abstract C–H bonds are ubiquitous and abundant in organic molecules. If such C–H bonds can be converted into the desired functional groups in a site-, chemo-, diastereo-, and enantio-selective manner, the functionalization of C–H bonds would be an efficient tool for step-, atom- and redox-economic organic synthesis. C–H oxidation, as a typical C–H functionalization, affords hydroxy and carbonyl groups, which are key functional groups in organic synthesis and biological chemistry, directly. Recently, significant developments have been made using non-heme-type transition-metal catalysts. Oxygen functional groups can be introduced to not only simple hydrocarbons but also complex natural products. In this paper, recent developments over the last fourteen years in non-heme-type complex-catalyzed C–H oxidations are reviewed. 1 Introduction 2 Regio- and Chemo-Selective C–H Oxidations 2.1 Tertiary Site-Selective C–H Oxidations 2.2 Secondary Site-Selective C–H Oxidations 2.3 C–H Oxidations of N-Containing Molecules 2.4 C–H Oxidations of Carboxylic Acids 2.5 Chemo- and Site-Selective Methylenic C–H Hydroxylations 3 Enantioselective C–H Oxidations 3.1 Desymmetrizations through C–H Oxidations 3.2 Enantiotopic Methylenic C–H Oxygenations 4 Conclusion