Biomimetic Cu/Nitroxyl Catalyst Systems for Selective Alcohol Oxidation

Abstract

The oxidation of alcohols to the corresponding carbonyl products is an important organic transformation and the products are used in a variety of applications. The development of catalytic methods for selective alcohol oxidation have garnered significant attention in an attempt to find a more sustainable method without any limitations. Copper, in combination with 2,2,6,6-tetramethyl-1-piperidine N-oxyl (TEMPO) and supported by organic ligands, have emerged as the most effective catalysts for selective alcohol oxidation and these catalyst systems are frequently compared to galactose oxidase (GOase). The efficiency of GOase has led to extensive research to mimic the active sites of these enzymes, leading to a variety of Cu/TEMPO· catalyst systems being reported over the years. The mechanistic pathway by which Cu/TEMPO· catalyst systems operate has been investigated by several research groups, which led to partially contradicting mechanistic description. Due to the disadvantages and limitations of employing TEMPO· as co-catalyst, alternative nitroxyl radicals or in situ formed radicals, as co-catalysts, have been successfully evaluated in alcohol oxidation. Herein we discuss the development and mechanistic elucidation of Cu/TEMPO· catalyst systems as biomimetic alcohol oxidation catalysts.