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Molecules 2018, 23(2), 412; https://doi.org/10.3390/molecules23020412

On the Reaction Mechanism of the 3,4-Dimethoxybenzaldehyde Formation from 1-(3′,4′-Dimethoxyphenyl)Propene

1
Chemistry Department, Pontifical Catholic University of Equator, Av. 12 de Octubre 1076 y Roca, Quito 170109, Ecuador
2
Center for Bioinformatics and Molecular Simulations, Faculty of Engineering, University of Talca, 2 Norte 685, Casilla 721, Talca 3640000, Chile
*
Authors to whom correspondence should be addressed.
Received: 22 December 2017 / Revised: 25 January 2018 / Accepted: 29 January 2018 / Published: 14 February 2018
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Abstract

Lignin peroxidase (LiP) is an important enzyme for degrading aromatic hydrocarbons not only in nature but also in industry. In the presence of H2O2, this enzyme can easily decompose lignin and analogue compounds under mild conditions. In this reaction mechanism, LiP catalyzes the C–C cleavage of a propenyl side chain, being able to produce veratraldehyde (VAD) from 1-(3′,4′-dimethoxyphenyl) propene (DMPP). One of the few and complete proposed mechanisms includes several non-enzymatic reactions. In this study, we performed a computational study to gain insight about the non-enzymatic steps involved in the reaction mechanism of VAD formation from DMPP using LiP as a catalyst. A kinetic characterization of the reaction using the reaction force and the reaction force constant concepts within the density functional theory (DFT) framework is proposed. All theoretical calculations for the reaction pathway were performed using the Minnesota Global Hybrid functional M06-2X and a 6-31++G(d,p) basis set. The complete reaction comprises seven steps (five steps not including LiP as a catalyst), which include radical species formation, bond transformation, water and oxygen addition, atom reordering, and deacetylation. The overall mechanism is an endothermic process with mixed activation energies depending on the four transition states. These results are the first attempt to fully understand the catalytic role of LiP in the degradation of lignin and its aromatic derivative compounds in terms of the electronic structure methods and future hybrid calculation approaches that we have recently been performing. View Full-Text
Keywords: lignin peroxidase; DFT; reaction force; force constant; reaction mechanism; 3,4-dimethoxybenzaldehyde; 1-(3′,4′-dimethoxyphenyl) propene lignin peroxidase; DFT; reaction force; force constant; reaction mechanism; 3,4-dimethoxybenzaldehyde; 1-(3′,4′-dimethoxyphenyl) propene
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Cuesta, S.; Arias, J.; Gallegos, F.; Alzate-Morales, J.; Meneses, L. On the Reaction Mechanism of the 3,4-Dimethoxybenzaldehyde Formation from 1-(3′,4′-Dimethoxyphenyl)Propene. Molecules 2018, 23, 412.

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