Copper/TEMPO Redox Redux: Analysis of PCET Oxidation of TEMPOH by Copper(II) and the Reaction of TEMPO with Copper(I).

ABSTRACT: Copper salts and organic aminoxyls, such as TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), are versatile catalysts for aerobic alcohol oxidation. Previous reports in the literature contain conflicting proposals concerning the redox interactions that take place between copper(I) and copper(II) salts with the aminoxyl and hydroxylamine species, TEMPO and TEMPOH, respectively. Here, we reinvestigate these reactions in an effort to resolve the conflicting claims in the literature. Under anaerobic conditions, Cu^IIX₂ salts [X = acetate (OAc), trifluoroacetate (TFA), and triflate (OTf)] are shown to promote the rapid proton-coupled oxidation of TEMPOH to TEMPO: Cu^IIX₂ + TEMPOH → Cu^IX + TEMPO + HX. In the reaction with acetate, however,

SUBMITTER: Ryan MC 

PROVIDER: S-EPMC7641458 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature