Interplay of Method Development and Mechanistic Studies – From Aerobic Oxidative Coupling to Radical Reactions via Alkenyl Peroxides

This account summarizes how scientific advances were made in the authors’ research group by combining method development in organic synthesis with detailed mechanistic studies. The discovery of an unexpected autoxidative coupling reaction led, by virtue of an ever increased understanding of its mechanism, to a strategy for green C–H functionalization reactions, novel modes of radical generation, addition reactions of ketones to alkenes and new insights into an old reaction, the Baeyer–Villiger oxidation. 1 Introduction 2 Aerobic Oxidative Coupling Reactions with Benzylic C–H Bonds 2.1 The Autoxidative Coupling with Xanthene 2.2 With a Little Help from Light – CHIPS 2.3 Related Autoxidative Coupling Reactions 3 How Does the Autoxidative Coupling Work? 3.1 An Excursion: Formation of Alkenyl Peroxides from Criegee Intermediates in the Atmosphere 3.2 How do Alkenyl Peroxides Form in Solution? Meet Criegee Again 3.3 The Full Mechanism of the Autoxidative Coupling Reaction 4 Previous Indications for Solution Chemistry of Alkenyl Peroxides 4.1 What Might Alkenyl Peroxides be Good for? 5 Concluding Remarks