27372-04-9Relevant academic research and scientific papers
A practical method for alcohol oxidation with aqueous hydrogen peroxide under organic solvent- and halide-free conditions
Sato, Kazuhiko,Aoki, Masao,Takagi, Junko,Zimmermann, Klaus,Noyori, Ryoji
, p. 2287 - 2306 (2007/10/03)
A catalytic system consisting of sodium tungstate and methyltrioctylammonium hydrogensulfate effects oxidation of simple secondary alcohols to ketones using 3 - 30% H2O2 without any organic solvents. The oxidation can be conducted under entirely halide-free, mildly acidic conditions. A combination of tungstic acid and an appropriate quaternary ammonium salt also effects the alcohol dehydrogenation. The organic/aqueous biphasic reaction allows easy product/catalyst separation. The turnover number, defined as tools of product per mol of catalyst, approaches 77700 (2- octanol) or 179000 (1-phenylethanol), two orders of magnitude higher than any previously reported. Ester, alkyl and t-butyldimethylsilyl ether, epoxy, carbonyl, N-alkyl carboxamide, and nitrile groups are tolerated under the reaction conditions. Secondary alcohols are preferentially oxidized over terminal olefins. Primary alkanols are oxidized directly to carboxylic acids in a moderate to high yield. Benzylic alcohols are selectively oxidized to benzaldehydes or benzoic acids under suitable conditions. This method is high-yielding, clean, safe, operationally simple, and cost-effective, and therefore suitable for practical organic synthesis. The mechanistic origin of the catalytic efficiency is discussed.
