A Thermodynamic Study of Ketoreductase-Catalyzed Reactions, Part 5. Reduction of Substituted Ketones in n-Hexane

Published

April 1, 2008

Author(s)

Yadu D. Tewari, David J. Vanderah, Michele M. Schantz, Robert N. Goldberg, J D. Rozzell, J F. Liebman, Raymond W. Hui, Yitzy Nissenbaum, Ahmad R. Parniani

Abstract

The equilibrium constants K for the ketoreductase-catalyzed reduction reactions of 1-benzyl-3-pyrrolidinone, ethyl 2-oxo-4-phenylbutyrate, ethyl 4-chloroacetoacetate, 1-benzyl-4-piperidone, and 1-benzyl-3-piperidone were measured in n-hexane at T = 298.15 K by using gas chromatography. The equilibrium constants for the reaction involving 1-benzyl-4-piperidone were also measured as a function of temperature (288.15 K to 308.05 K). The calculated thermodynamic quantities for the reaction (1-benzyl-4-piperidone + 2-propanol = 1-benzyl-4-hydroxypiperidine + acetone) reaction carried out in n-hexane at T = 298.15 K are: K = (26.2 1.7); DrG m = (8.10 0.16) kJ mol-1; DrH m = (3.44 0.42) kJ mol-1; and DrS m = (15.6 1.4) J K-1 mol-1. The chirality of the hydroxyl products of the reactions (1), (2), (3) and (5) has also been investigated. The results showed that the stereoselectivity of the hydroxyl products formed can be controlled by the selection of the solvent and enzyme used in these reactions. The thermochemical results for these reactions have been compared with the results for reactions that have analogous structural features and with the results of quantum chemical calculations.

Citation

Journal of Chemical Thermodynamics

Volume

40

Issue

4

Pub Type

Journals

Keywords

1-benzyl-3-piperidone, 1-benzyl-3-pyrrolidinone, 1-benzyl-4-piperidone, enthalpy, equilibrium constant, ethy 4-chloroacetoacetate, ethyl 2-oxo-4-phenylbutyrate, ketoreducatase

Citation

Tewari, Y. , Vanderah, D. , Schantz, M. , Goldberg, R. , Rozzell, J. , Liebman, J. , Hui, R. , Nissenbaum, Y. and Parniani, A. (2008), A Thermodynamic Study of Ketoreductase-Catalyzed Reactions, Part 5. Reduction of Substituted Ketones in n-Hexane, Journal of Chemical Thermodynamics (Accessed April 23, 2024)