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Mechanisms of the Aerobic Oxidation of Alcohols to Aldehydes and Ketones, Catalysed under Mild Conditions by Persistent and Non‐Persistent Nitroxyl Radicals and Transition Metal Salts − Polar, Enthalpic, and Captodative Effects
Author(s) -
Minisci Francesco,
Recupero Francesco,
Cecchetto Andrea,
Gambarotti Cristian,
Punta Carlo,
Faletti Roberta,
Paganelli Roberto,
Pedulli Gian Franco
Publication year - 2004
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200300332
Subject(s) - chemistry , nitroxyl , thermochemistry , radical , polar , alcohol oxidation , catalysis , transition metal , kinetics , oxygen , organic chemistry , photochemistry , inorganic chemistry , quantum mechanics , physics , astronomy
The oxidation of alcohols to aldehydes and ketones by air or oxygen under mild conditions (room temperature and atmospheric pressure), catalysed by persistent and non‐persistent nitroxyl radicals in combination with transition metal salts, appears to be the most convenient of the numerous processes developed for these purposes. The thermochemistry, the kinetics, and the Hammett correlations have allowed us to establish, on a quantitative basis, the fundamental difference between the oxidation catalysed by persistent and non‐persistent nitroxyl catalysts. In the latter case, an interesting significant captodative effect is displayed for the first time for the oxidation of substituted benzyl alcohols; the importance of enthalpic and polar effects is emphasised. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)