Efficient and Selective Aerobic Oxidation of Alcohols into Aldehydes and Ketones Using Ruthenium/TEMPO as the Catalytic System
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- 21 June 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 123 (28) , 6826-6833
- https://doi.org/10.1021/ja0103804
Abstract
The combination of RuCl2(PPh3)3 and TEMPO affords an efficient catalytic system for the aerobic oxidation of a variety of primary and secondary alcohols, giving the corresponding aldehydes and ketones, in >99% selectivity in all cases. The Ru/TEMPO system displayed a preference for primary vs secondary alcohols. Results from Hammett correlation studies (ρ = −0.58) and the primary kinetic isotope effect (kH/kD = 5.1) for the catalytic aerobic benzyl alcohol oxidations are inconsistent with either an oxoruthenium (ORu) or an oxoammonium based mechanism. We postulate a hydridometal mechanism, involving a “RuH2(PPh3)3” species as the active catalyst. TEMPO acts as a hydrogen transfer mediator and is either regenerated by oxygen, under catalytic aerobic conditions, or converted to TEMPH under stoichiometric anaerobic conditions.Keywords
This publication has 33 references indexed in Scilit:
- Oxidation of Primary Alcohols to Carboxylic Acids with Sodium Chlorite Catalyzed by TEMPO and BleachThe Journal of Organic Chemistry, 1999
- Dioxygen Oxidation of Alcohols and Aldehydes Over a Cerium Dioxide-Ruthenium SystemSynthetic Communications, 1998
- Kinetic Resolution of Racemic Secondary Alcohols by RuII‐Catalyzed Hydrogen TransferAngewandte Chemie International Edition in English, 1997
- Ruthenium-Catalyzed Oxidation of Nonactivated Alcohols by MnO2The Journal of Organic Chemistry, 1994
- Prganic Nitrosonium Salts as Oxidants in Organic ChemistryHETEROCYCLES, 1988
- Cycloaddition reactions of a bisisobenzofuran leading to linear polyacenequinones and a quadruply bridged cyclophaneThe Journal of Organic Chemistry, 1987
- The selective oxidation of primary alcohols to aldehydes by oxygen employing a trinuclear ruthenium carboxylate catalystJournal of the American Chemical Society, 1987
- Use of Ruthenium Tetroxide as a Multi-purpose OxidantJournal of the American Chemical Society, 1958
- Solid Manganese Dioxide as an Oxidizing AgentJournal of the American Chemical Society, 1955
- Enzymatic Synthesis of the Enantiomorphis of Ethanol-1-d1,2Journal of the American Chemical Society, 1953