Palladium-catalyzed aerobic alcohol oxidation supported by a new type of α-diimine ligands

Jin Zhou; Xiaoyan Li; Hongjian Sun
August 2008
Canadian Journal of Chemistry;Aug2008, Vol. 86 Issue 8, p782
Academic Journal
A series of new ionic sulfonated α-diimine ligands were prepared and employed as supporting ligands for the palladium-catalyzed aerobic alcohol oxidation. The electronic properties, rigidity, and steric hindrance of ligands have remarkable influences upon the catalytic activity of the palladium complexes. The best catalytic result could be achieved using ligand 9 with an electron-withdrawing sulfonyl substituent together with bulky groups (iso-propyl in 2,6-positions). This diimine/palladium-catalyzed system is highly efficient for the oxidation of various benzylic alcohols, and showed moderate yields for the secondary aliphatic alcohols and cyclic alcohols.Key words: α-diimine, palladium, aerobic oxidation, alcohol. On a préparé une série de nouveaux ligands ioniques α-diimines sulfonées et on les a utilisés comme ligands de support pour des réactions d’oxydation aérobiques d’alcools catalysées par le palladium. Les propriétés électroniques, la rigidité et l’empêchement stérique des ligands influencent profondément l’activité catalytique des complexes du palladium. Le meilleur résultat catalytique a été obtenu en utilisant le ligand 9 qui porte un substituant électroaffinitaire sulfonyle avec des substituants volumineux, isopropyles, dans les positions 2 et 6. Ce système de diimine catalysée par le palladium est très efficace pour l’oxydation de divers alcools benzyliques et donne des rendements modérés avec les alcools aliphatiques ou cycliques secondaires.Mots-clés : α-diimine, palladium, oxydation aérobique, alcool.[Traduit par la Rédaction]


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