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

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.