Chemoselective Oxidation by Electronically Tuned Nitroxyl Radical Catalysts


  • We are grateful to Prof. Norihiro Tokitoh and Dr. Takahiro Sasamori for generous assistance to the measurement of cyclic voltammetry. This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Advanced Molecular Transformation by Organocatalysts” from The Ministry of Education, Culture, Sports, Science and Technology (Japan), and by Grant-in-Aid for JSPS Fellows to S.H.


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Electronic tuning: Nitroxyl radical 1 is shown to be an efficient catalyst for the oxidation of secondary alcohols, and promotes oxidation through an oxoammonium species which is highly reactive because of the adjacent electron-withdrawing ester groups. Chemoselective oxidation of benzylic alcohols in the presence of aliphatic alcohols is observed and is proposed to proceed by a rate-determining hydride transfer.