Mixed‐Electrolyte‐Driven Stereoselective Electrochemical Glycosylation

Mixed electrolytes such as tetrabutylammonium triflate (Bu 4 NOTf) and tetrabutylammonium bis(trifluoromethanesulfonyl‐amide) (Bu 4 NNTf 2 ) were found to improve stereoselectivity in electrochemical glycosylation of thioglycosides building blocks without a stereocontrolling group. Bu 4 NOTf was crucial to generate glycosyl triflate intermediate, whereas a second electrolyte such as Bu 4 NNTf 2 contributes reducing solution resistance. Therefore, we assume that Bu 4 NOTf works as a reservoir of the triflate anion of the glycosyl triflate intermediate and Bu 4 NNTf 2 works only as an electrolyte.