151636-14-5Relevant articles and documents
Combined ruthenium(II) and lipase catalysis for efficient dynamic kinetic resolution of secondary alcohols. Insight into the racemization mechanism
Martin-Matute, Belen,Edin, Michaela,Bogar, Krisztian,Kaynak, F. Betuel,Baeckvall, Jan-E.
, p. 8817 - 8825 (2007/10/03)
Pentaphenylcyclopentadienyl ruthenium complexes (3) are excellent catalysts for the racemization of secondary alcohols at ambient temperature. The combination of this process with enzymatic resolution of the alcohols results in a highly efficient synthesis of enantiomerically pure acetates at room temperature with short reaction times for most substrates. This new reaction was applied to a wide range of functionalized alcohols including heteroaromatic alcohols, and for many of the latter, enantiopure acetates were efficiently prepared for the first time via dynamic kinetic resolution (DKR). Different substituted cyclopentadienyl ruthenium complexes were prepared and studied as catalysts for racemization of alcohols. Pentaaryl-substituted cyclopentadienyl complexes were found to be highly efficient catalysts for the racemization. Substitution of one of the aryl groups by an alkyl group considerably slows down the racemization process. A study of the racemization of (S)-1-phenylethanol catalyzed by ruthenium hydride η5-Ph5CpRu(CO) 2H (8) indicates that the racemization takes place within the coordination sphere of the ruthenium catalyst. This conclusion was supported by the lack of ketone exchange in the racemization of (S)-1-phenylethanol performed in the presence of p-tolyl methyl ketone (1 equiv), which gave 1% of 1-(p-tolyl)ethanol. The structures of ruthenium chloride and iodide complexes 3a and 3c and of ruthenium hydride complex 8 were confirmed by X-ray analysis.
Ruthenium- and enzyme-catalyzed dynamic kinetic resolution of secondary alcohols
Persson, B. Anders,Larsson, Anna L. E.,Le Ray, Mika?l,B?ckvall, Jan-E.
, p. 1645 - 1650 (2007/10/03)
Enzymatic resolution of secondary alcohols under substrate racemizing conditions was studied using an immobilized lipase from Candida antarctica in the presence of a ruthenium catalyst. A specifically designed acyl donor, 4- chlorophenyl acetate, was found to be compatible with both catalysts and resulted in an efficient dynamic kinetic resolution. Studies of the reaction in different solvents showed that nonpolar solvents gave the best results. With this process, a variety of racemic secondary alcohols were transformed to the corresponding enantiomerically pure acetates, making efficient use of all starting material. In most cases, the reaction proceeded with >99% ee and in good yield.
