Oxidase Catalysis via an Aerobically Generated Dess-Martin Periodinane Analogue

Hypervalent iodine(V) reagents, such as Dess-Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis. Development of strategies to access these reagents from O2 would immediately enable use of O2 as a terminal oxidant in a broad array of substrate oxidation reactions. Recently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. Here, we couple aerobic oxidation of iodobenzenes with disproportionation of the initially generated I(III) compounds to generate I(V) reagents. The aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP. Further, the developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.