Application and mechanistic studies of a water-oxidation catalyst in alcohol oxidation by employing oxygen-transfer reagents
2012 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 18, no 52, 16947-16954 p.Article in journal (Refereed) Published
By using a dimeric ruthenium complex in combination with tert-butyl hydrogen peroxide (TBHP) as stoichiometric oxidant, a mild and efficient protocol for the oxidation of secondary benzylic alcohols was obtained, thereby giving the corresponding ketones in high yields within 4 h. However, in the oxidation of aliphatic alcohols, the TBHP protocol suffered from low conversions owing to a competing Ru-catalyzed disproportionation of the oxidant. Gratifyingly, by switching to Oxone (2 KHSO5⋅KHSO4⋅K2SO4 triple salt) as stoichiometric oxidant, a more efficient and robust system was obtained that allowed for the oxidation of a wide range of aliphatic and benzylic secondary alcohols, giving the corresponding ketones in excellent yields. The mechanism for these reactions is believed to involve a high-valent RuV–oxo species. We provide support for such an intermediate by means of mechanistic studies.
Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2012. Vol. 18, no 52, 16947-16954 p.
alcohols, biphasic catalysis, oxidation, Oxone, ruthenium
IdentifiersURN: urn:nbn:se:su:diva-86521DOI: 10.1002/chem.201202266OAI: oai:DiVA.org:su-86521DiVA: diva2:587176
FunderKnut and Alice Wallenberg Foundation