Oppenauer-type oxidation of secondary alcohols catalyzed by homogeneous water-soluble complexes

The catalytic system composed of [Ir(COD)Cl] 2 , 2,2′-biquinoline-4,4′-dicarboxylic acid dipotassium salt (BQC), and sodium carbonate is highly efficient for the selective oxidation of benzylic, 1-heteroaromatic, aliphatic, and allylic secondary alcohols using catalyst:substrate ratios ranging from...

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Bibliographic Details
Published inCanadian journal of chemistry Vol. 83; no. 6-7; pp. 702 - 710
Main Authors Ajjou, Abdelaziz Nait, Pinet, Jean-Louis
Format Journal Article
LanguageEnglish
Published Ottawa, Canada NRC Research Press 01.06.2005
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Summary:The catalytic system composed of [Ir(COD)Cl] 2 , 2,2′-biquinoline-4,4′-dicarboxylic acid dipotassium salt (BQC), and sodium carbonate is highly efficient for the selective oxidation of benzylic, 1-heteroaromatic, aliphatic, and allylic secondary alcohols using catalyst:substrate ratios ranging from 0.4% to 2.5%. Sterically hindered allylic alcohols undergo selectively good conversions to the corresponding enones, while unhindered ones are completely isomerized to saturated ketones. Mercury tests indicate that the catalytic process is likely homogeneous. The mechanism proposed for this Oppenauer-type oxidation including the isomerization process is based on iridium-alkoxide species.Key words: Oppenauer oxidation, water, catalysis, isomerization, secondary alcohols.
ISSN:0008-4042
1480-3291
DOI:10.1139/v05-037