Oppenauer Oxidation-百灵威

The oxidation of primary and secondary alcohols with ketones in the presence of metal alkoxides such as aluminum isopropoxide (Al(i-PrO)₃) to yield aldehydes and ketones is known as the Oppenauer oxidation. The alcohol substrate binds to aluminum, and the ketone coordinates to it, forming a six-membered transition state that allows the alkoxide to transfer a hydride to the ketone, yielding a ketone and an i-propyl alcohol respectively. The reaction is reversible, favoring a large excess of the starting ketone.

Reagents: Metal Alkoxides (e.g. Aluminum Isopropoxide, t-Butoxide, or Phenoxide), Carbonyl Compound Oxidant (e.g. Acetone)
Reactant: Alkyl, Aryl, Alkenyl 1° or 2° Alcohol
Product: Ketone or Aldehyde, i-Propyl Alcohol
Type of Reaction: Oxidation

Mechanism

Original Paper

Oppenauer, R. V. Eine Methode der Dehydrierung von Sekundären Alkoholen zu Ketonen. I. Zur Herstellung von Sterinketonen und Sexualhormonen. Recueil des Travaux Chimiques des Pays-Bas 1937, 56 (2), 137-144.

Top Citations

The Oppenauer Oxidation. In Organic Reactions; American Cancer Society, 2011; pp 207-272.

The Mg-Oppenauer Oxidation as a Mild Method for the Synthesis of Aryl and Metallocenyl Ketones. Chemistry – A European Journal 2007, 13 (1), 215-227.

Tishchenko Reactions and Oppenauer Oxidation Reactions of Aldehydes Promoted by Diisobutylaluminum Hydride. Tetrahedron Letters 2004,45 (16), 3313-3315.

Related Reactions

Meerwein-Ponndorf-Verley

Tishchenko Reaction

Synthesis of Aldehydes

Synthesis of Ketones

Related Compounds

Al(OiPr)₃ (CAS 555-31-7)