Efficient aerobic ruthenium-catalyzed oxidation of secondary alcohols by the use of a hybrid electron transfer catalyst
2010 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 10, 1971-1976 p.Article in journal (Refereed) Published
Biomimetic aerobic oxidation of secondary alcohols has been performed using hybrid catalyst 1 and Shvo's catalyst 2. This combination allows mild reaction conditions and low catalytic loading, due to the efficiency of intramolecular electron transfer. By this method a wide range of different alcohols have been converted into their corresponding ketones. Oxidation of benzylic as well as aliphatic, electron-rich, electron-deficient and sterically hindered alcohols could be oxidized in excellent yield and selectivity. Oxidation of (S)-1-phenyl-ethanol showed that no racemization occurred during the course of the reaction, indicating that the hydride 2b adds to the quinone much faster than it re-adds to the ketone product. The kinetic deuterium isotope effect of the oxidation was determined by the use of 1-phenylethanol (3a) and 1-deuterio-1-phenylethanol (3a-d1) in parallel and competitive manner, which gave the same isotope effect within experimental error (k(H)/k(D) approximate to 2.8). This indicates that there is no strong coordination of the substrate to the catalyst.
Place, publisher, year, edition, pages
2010. no 10, 1971-1976 p.
Oxidation, Alcohols, Electron transfer, Hybrid catalysts, Ruthenium
Research subject Organic Chemistry
IdentifiersURN: urn:nbn:se:su:diva-45863DOI: 10.1002/ejoc.201000033ISI: 000276742400017OAI: oai:DiVA.org:su-45863DiVA: diva2:370106
FunderKnut and Alice Wallenberg FoundationSwedish Research Council
authorCount :52010-11-152010-11-152011-12-02Bibliographically approved