Selective Aerobic Oxidation of Alcohols in Low Melting Mixtures and Water and Use for Telescoped One-Pot Hybrid Reactions

An efficient, selective and sustainable protocol was developed for the CuCl2/TEMPO/TMEDA-catalyzed aerobic oxidation of activated alcohols to the corresponding carbonyl compounds using water or the environmentally friendly low melting mixture (LMM) d-fructose-urea as the reaction medium. Such oxidation reactions proceed under mild (room temperature or 40 degrees C) and aerobic conditions, with the carbonyl derivatives isolated in up to 98 % yield and within 4 h reaction time when using the above-mentioned LMM. The potential application of this methodology is demonstrated by setting up useful telescoped, one-pot two-step hybrid transformations for the direct conversion of primary alcohols either into secondary alcohols or into valuable nitroalkenes, by combining oxidation processes with nucleophilic additions promoted by highly polarized organometallic compounds (Grignard and organolithium reagents) or with nitroaldol (Henry) reactions, respectively.