73959-37-2Relevant academic research and scientific papers
ENZYMATIC "IN VITRO" REDUCTION OF KETONES. VI.(1) Reduction rates and stereochemistry of the HLAD-catalyzed reduction of 3-alkyl- and 4-alkylcyclohexanones.
Osselaer, T. A. Van,Lemiere, G. L.,Lepoivre, J. A.,Alderweireldt, F. C.
, p. 133 - 150 (2007/10/02)
Reaction rate constants for the catalytic step HLAD-NADH + ketone * HLAD-NAD+ + alcohol in the HLAD-catalyzed reduction of 3-alkyl- and 4-alkylcyclohexanones are determined from initial rate measurements in the coenzyme recycling system ketone-ethanol-NAD+-HLAD.By rate measurements at several temperatures, activation parameters were determined and isokinetic relationships tracked down.Two different isokinetic relationships show that the 3-alkylcyclohexanones pass through an other type of transition state than cyclohexanone and the 4-alkylcyclohexanones, which means that they have a different arrangement on the HLAD-NADH complex.The results are rationalized in view of the most recent principles on nucleophilic additions to carbonyl functions.The resulting model for the HLAD-catalyzed reduction adequately explains the observed rate accelerating and decelerating effects and the stereochemistry of the reduction as well.
