An Environmentally Benign TEMPO-Catalyzed Efficient Alcohol Oxidation System with a Recyclable Hypervalent Iodine(III) Reagent and Its Facile Preparation

Abstract

A highly efficient 2,2,6,6-tetramethylpiperidin-1-yloxy (TEMPO) catalyzed alcohol oxidation system using recyclable 1-chloro-1,2-benziodoxol-3(1H)-one as the terminal oxidant in ethyl acetate, which is an environmentally friend organic solvent, at room temperature has been developed. A variety of alcohols can be oxidized to their corresponding carbonyl compounds in high to excellent yields. Various heteroaromatic rings and C=C bonds are well tolerated under the reaction conditions. 1-Chloro-1,2-benziodoxol-3(1H)-one can be easily recycled after simple solid/liquid-phase separation and the subsequent regeneration sequence. In addition, a safe, very convenient, large-scale, and high-yielding procedure for the preparation of 1-chloro-1,2-benziodoxol-3(1H)-one from 2-iodobenzoic acid has been developed using sodium chlorite as the stoichiometric oxidant in dilute hydrochloric acid at room ­temperature.

Key words

alcohol - hypervalent iodine - oxidation - recyclable - TEMPO

References

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  However, the possibility of pyridine being a nucleophile in the present reaction could be ruled out since oxidant 1 was recovered more than 90% after stirring the mixture of 1 and pyridine with or without TEMPO in EtOAc for much longer time (24 h) than that required for the alcohol oxidation (0.5 to 9 h). Notably, other organic bases such as triethylamine and DMAP which could also be used as acid scavengers destroyed the oxidant 1 which was confirmed by two control experiments.

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17

Radical A or A′ was suggested to be a poor oxidant towards TEMPO by trapping experiments using TEMPO performed by Ochiai et al. in their oxidation of the benzylic and allylic ether by stable hypervalent (tert-butylperoxy)iodanes via benzylic and allylic radicals in which radical A or A′ was employed as a highly efficient hydrogen-abstracting species (ref. 14b). On the other hand, the oxidation of TEMPO by chlorine atom is well established (refs. 9a and 15). Therefore, we proposed that radical A′ could oxidize hydroxylamine C to TEMPO via a hydrogen-abstracting step.