O ‐ C Glycoside Rearrangement through Time‐Controlled Electrochemical Flow Strategy: Switching between Kinetics and Thermodynamics

Abstract We herein report time‐controlled O ‐ C glycoside rearrangement in flow‐electrochemical microreactors, focusing on kinetic and thermodynamic selectivity. The selective synthesis of phenolic O ‐ and C ‐glycosides has been explored using O ‐ C glycoside rearrangement. We investigated the time‐control of O ‐ C glycoside rearrangement using a flow microreactor, which allows for second‐scale reaction control. The electrochemical approach demonstrated that shortening the residence time leads to the selective synthesis of O ‐glycosides, while longer times favor the formation of C ‐glycosides. Kinetic studies revealed that substituents on the phenol ring affect the rate of O ‐glycoside formation and its rearrangement to C ‐glycosides. Finally, continuous flow synthesis was demonstrated, showcasing the scalability and utility of this method for producing bioactive substances.