Mechanistic insight into aerobic alcohol oxidation using NOx-nitroxide catalysis based on catalyst structure-activity relationships

Masatoshi Shibuya, Shota Nagasawa, Yuji Osada, Yoshiharu Iwabuchi

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)

Abstract

The mechanism of an NOx-assisted, nitroxide(nitroxyl radical)-catalyzed aerobic oxidation of alcohols was investigated using a set of sterically and electronically modified nitroxides (i.e., TEMPO, AZADO (1), 5-F-AZADO (2), 5,7-DiF-AZADO (3), 5-MeO-AZADO (4), 5,7-DiMeO-AZADO (5), oxa-AZADO (6), TsN-AZADO (7), and DiAZADO (8)). The motivation for the present study stemmed from our previous observation that the introduction of an F atom at a remote position from the nitroxyl radical moiety on the azaadamantane nucleus effectively enhanced the catalytic activity under typical NOx-mediated aerobic-oxidation conditions. The kinetic profiles of the azaadamantane-N-oxyl-[AZADO (1)-, 5-F-AZADO (2)-, and 5,7-DiF-AZADO (3)]-catalyzed aerobic oxidations were closely investigated, revealing that AZADO (1) showed a high initial reaction rate compared to 5-F-AZADO (2) and 5,7-DiF-AZADO (3); however, AZADO-catalyzed oxidation exhibited a marked slowdown, resulting in ∼90% conversion, whereas 5-F-AZADO-catalyzed oxidation smoothly reached completion without a marked slowdown. The reasons for the marked slowdown and the role of the fluoro group are discussed. Oxa-AZADO (6), TsN-AZADO (7), and DiAZADO (8) were designed and synthesized to confirm their comparable catalytic efficiency to that of 5-F-AZADO (2), providing supporting evidence for the electronic effect on the catalytic efficiency of the heteroatoms under NOx-assisted aerobic-oxidation conditions.

Original languageEnglish
Pages (from-to)10256-10268
Number of pages13
JournalJournal of Organic Chemistry
Volume79
Issue number21
DOIs
Publication statusPublished - 2014 Nov 7

ASJC Scopus subject areas

  • Organic Chemistry

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