Structure-reactivity relationship of piperidine nitroxide: Electrochemical, ESR and computational studies

Toshihide Yamasaki, Fumiya Mito, Yuko Ito, Sokkar Pandian, Yuichi Kinoshita, Koji Nakano, Ramachandran Murugesan, Kiyoshi Sakai, Hideo Utsumi, Ken Ichi Yamada

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

We have synthesized several nitroxides with different substituents which vary the steric and electronic environment around the N-O moiety and have systematically investigated the role of substituents on the stability of the radicals. Our results demonstrated the reactivity toward ascorbate correlates with the redox potential of the derivatives. Furthermore, ab initio calculations also indicated a correlation between the reduction rate and the computed singly occupied molecular orbital-lowest unoccupied molecular orbital energy gap, but not with solvent accessible surface area of the N-O moiety, supporting the experimental results and suggesting that the electronic factors largely determine the radicals' stability. Hence, it is possible to perform virtual screening of nitroxides to optimize their stability, which can help to rationally design novel nitroxides for their potential use in vivo.

Original languageEnglish
Pages (from-to)435-440
Number of pages6
JournalJournal of Organic Chemistry
Volume76
Issue number2
DOIs
Publication statusPublished - Jan 21 2011

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All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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