Electrochemical Synthesis of Imino‐ C ‐Nucleosides by “Reactivity Switching” Methodology for in situ Generated Glycoside Donors

Redox‐induced regioselective C(sp 3 )‐H C ‐glycosidation for unactivated prolinols was achieved by controlling the anomeric reactivity of electrochemically generated iminium cations. A mechanistic study revealed that the intermediate was pooled as covalent azaribose or iminium cation species in situ , and the electrophilicity of intermediates can be adjusted by changing coexisting acids. We found that the armed/disarmed analogy concept of traditional glycochemistry can be adapted to our C ‐glycosidation reaction. Finally, we invented a logical synthetic methodology, named “reactivity switching” concept, and synthesized a series of imino‐ C ‐nucleosides ( C ‐azanucleosides) based on this methodology.