Mechanism and rate constant of proline-catalysed asymmetric aldol reaction of acetone and p-nitrobenzaldehyde in solution medium: Density-functional theory computation

Journal of Advanced Research
Usman I TafidaStephen E Abechi

Abstract

In search of new ways to improve catalyst design, the current research focused on using quantum mechanical descriptors to investigate the effect of proline as a catalyst for mechanism and rate of asymmetric aldol reaction. A plausible mechanism of reaction between acetone and 4-nitrobenzaldehyde in acetone medium was developed using highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies calculated via density functional theory (DFT) at the 6-31G∗/B3LYP level of theory. New mechanistic steps were proposed and found to follow, with expansion, the previously reported iminium-enamine route of typical class 1 aldolase enzymes. From the elementary steps, the first step which involves a bimolecular collision of acetone and proline was considered as the rate-determining step, having the highest activation energy of 59.07 kJ mol-1. The mechanism was used to develop the rate law from which the overall rate constant was calculated and found to be 4.04 × 10 - 8 d m 3 mol - 1 s - 1 . The new mechanistic insights and the explicit computation of the rate constant further improve the kinetic knowledge of the reaction.

Citations

Jun 15, 2021·The Journal of Organic Chemistry·Li-Juan Yu, Michelle L Coote
Sep 7, 2018·The Journal of Physical Chemistry. a·Pei-Huan ZhangZuo-Yin Yang
Mar 26, 2019·The Journal of Organic Chemistry·Charitha GurugeNasri Nesnas

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