A Simplified Approach for Electrochemical Allylic Oxidation of Olefins

Abstract A simple method for the electrochemical allylic oxidation of olefins to enones based on peroxide‐mediated C–H activation is presented. t ‐Butyl hydroperoxide serves a dual role as mediator and oxygen source, avoiding the utilization of expensive transition metal catalysts, potentially explosive supporting electrolytes such as perchlorates, or additional environmentally harmful mediators. This elegant methodology allows for an operationally simple and sustainable late‐stage transformation of delicate natural compounds such as terpenes or steroids into highly value‐added building blocks. Such an approach provides a greener alternative to conventional oxidation methods used for industrial applications. In total, 25 examples are demonstrated with isolated yields up to 80%. The robust scalability of the method was also demonstrated, and chromatography could be avoided in scale‐up simply by using recrystallization, which decreases the cost of downstream processing.