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Electrochemical Synthesis of Imino‐ C ‐Nucleosides by “Reactivity Switching” Methodology for in situ Generated Glycoside Donors
Author(s) -
Okamoto Kazuhiro,
Tsutsui Mizuki,
Morizumi Haruka,
Kitano Yoshikazu,
Chiba Kazuhiro
Publication year - 2021
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202100106
Subject(s) - iminium , chemistry , reactivity (psychology) , regioselectivity , electrophile , electrochemistry , redox , combinatorial chemistry , in situ , anomer , stereochemistry , organic chemistry , ion , catalysis , electrode , medicine , alternative medicine , pathology
Abstract 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.