Modeling the mechanism of glycosylation reactions between ethanol, 1,2-ethanediol and methoxymethanol

Azofra, Luis Miguel; Alkorta, Ibón; Toro–Labbé, Alejandro; Elguero, José

doi:10.1039/c3cp51963e

Cited by 7 publications

(4 citation statements)

References 48 publications

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“…All these points define the energy profile, E, of a chemical reaction; however, such energy profile does not give complete information about the reaction mechanism, and therefore, it is convenient to consider the reaction force, F (Eq. 3), defined as the negative derivative of the total energy with respect the reaction coordinate, ξ [43][44][45][46]: Also, other interesting property is the electronic chemical potential, μ (Eq. 4), which for a N-electronic system is defined as the derivative of the energy with respect the number of electrons when the external potential, v( − → r ), remains constant:…”

Section: Theoretical Frameworkmentioning

confidence: 99%

Ab initio study in the hydration process of metaphosphoric acid: the importance of the pnictogen interactions

2015

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known that the inorganic phosphorus oxoacids are one of the many systems which experiment such reaction (and its reverse one, dehydration) when transformed in the different oxoacid species. In the present paper, our efforts were concentrated on the study of the hydration reaction of metaphosphoric acid (HPO 3), a water-or moisture-absorbing reagent that, upon water absorption, evolves to orthophosphoric, also known as phosphoric acid (H 3 PO 4). The dehydration of H 3 PO 4 to HPO 3 in aqueous solution has been measured experimentally as 134 ± 8 kJ mol −1 [2]. Also, dehydration of the protonated phosphoric acid has been studied theoretically, and the proton affinity of HPO 3 has been calculated to be 712 kJ mol −1 at the G2(MP2) computational level [3]. In addition, hydrolysis of different phosphorus derivatives as phosphate anion [4], phosphate monoesters [5] and phosphate diesters and triesters [6] has been studied computationally. The protonation and dehydration of the protonated form of orthophosphoric acid have been studied experimentally and theoretically [3]. Finally, in 2002, Davies et al. estimated the pK a values of pentaoxyphosphoranes based on single bonds lengths [7], and more recently, the study of pnictogen (or pnicogen)-bonded complexes of the related PO 2 X (X = F, Cl and Br) compounds with electron donors reveals the great power of P as electron acceptor [8, 9]. In the present work, we will analyze the reaction mechanism of the hydration of metaphosphoric acid, focusing on the key role the number of explicit water molecules play as reactants or bridges in the assistance of the proton transfer, as well as the importance of the pnictogen interactions [1, 8-23], which are noncovalent forces [24] of electrostatic nature which favor bounded connections between negative entities with positive holes [25] (in their σ or π nature) located on the pnictogen atoms (N, P, As and Sb).

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Section: Theoretical Frameworkmentioning

confidence: 99%

Ab initio study in the hydration process of metaphosphoric acid: the importance of the pnictogen interactions

2015

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“…Conceptual DFT (CDFT) offers a series of theoretical tools that allow an analysis of the intrinsic reactivity for chemical events occurring at the electronic level and being directly associated with physicochemical properties of both global and local nature. A detailed explanation of the Conceptual DFT descriptors can be found in the very rich literature on the subject, among which we highlight some of our works in the field. − Notwithstanding, it is convenient to proceed with a brief review of those main descriptors that we will use in the present article. When the energy of a given chemical process is represented along the intrinsic reaction coordinate (IRC or ξ), the ξ R , ξ TS , and ξ P values represent the points of the IRC in which are located reactant (R), transition state (TS), and product (P), respectively.…”

Section: Introductionmentioning

confidence: 99%

A Conceptual DFT Study of Phosphonate Dimers: Dianions Supported by H-Bonds

2020

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A conceptual DFT study of the dissociation of anionic and neutral phosphonate dimers has been carried out. In addition, the dianion complexes have been studied in the presence of two solvents, water and tetrahydrofuran. The dissociation of the dianion complexes in the gas phase and in solution present a maximum along the reaction coordinate that is not present in the neutral−neutral and anion−neutral complexes. The principal chemical descriptors (chemical potential, reaction electronic flux, hardness, and global electrophilicity index) do not show changes in their trends along the dissociation profiles even when there is an energy maximum in the case of the anion−anion complexes.

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“…Conceptual DFT (CDFT) provides a series of hierarchy chemical concepts that allow an analysis of the chemical reactivity directly associated with physicochemical properties of both global and local nature [ 42 , 43 ]. Amongst the contributors to this methodology, Prof Toro-Labbé has shown its utility in an important number of chemical reactions [ 44 ], including the reinterpretation of the Woodward–Hoffmann rules [ 45 ], glycosylation reactions [ 46 , 47 ], reactivity of hydrogenases [ 48 ], reduction of carbon dioxide [ 49 ], and expanded its application to the atomic level [ 50 ] as well as developing the theory of bond reactivity [ 51 ].…”

Section: Introductionmentioning

confidence: 99%

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Ferrer,

Elguero,

Alkorta

et al. 2024

J Mol Model

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Context A Conceptual DFT (CDFT) study has been carry out to analyse the coupling reactions of the simplest amine (CH3NH2), alcohol (CH3OH), and thiol (CH3SH) compounds with CO2 to form the corresponding adducts CH3NHCO2H, CH3OCO2H, and CH3SCO2H. The reaction mechanism takes place in a single step comprising two chemical events: nucleophilic attack of the non-metallic heteroatoms to CO2 followed by hydrogen atom transfer (HAT). According to our calculations, the participation of an additional nucleophilic molecule as HAT assistant entails important decreases in activation electronic energies. In such cases, the formation of a six-membered ring in the transition state (TS) reduces the angular stress with respect to the non-assisted paths, characterised by four-membered ring TSs. Through the analysis of the energy and reaction force profiles along the intrinsic reaction coordinate (IRC), the ratio of structural reorganisation and electronic rearrangement for both activation and relaxation energies has been computed. In addition, the analysis of the electronic chemical potential and reaction electronic flux profiles confirms that the highest electronic activity as well as their changes take place in the TS region. Finally, the distortion/interaction model using an energy decomposition scheme based on the electron density along the reaction coordinate has been carried out and the relative energy gradient (REG) method has been applied to identify the most important components associated to the barriers. Methods The theoretical calculation were performed with Gaussian-16 scientific program. The B3LYP-D3(BJ)/aug-cc-pVDZ level was used for optimization of the minima and TSs. IRC calculations has also been carried out connecting the TS with the associated minima. Conceptual-DFT (CDFT) calculations have been carried out with the Eyringpy program and in-house code. The distortion/interaction model along the reaction coordinate have used the decomposition scheme of Mandado et al. and the analysis of the importance of each components have been done with the relative energy gradient (REG) method.

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Modeling the mechanism of glycosylation reactions between ethanol, 1,2-ethanediol and methoxymethanol

Cited by 7 publications

References 48 publications

Ab initio study in the hydration process of metaphosphoric acid: the importance of the pnictogen interactions

Ab initio study in the hydration process of metaphosphoric acid: the importance of the pnictogen interactions

A Conceptual DFT Study of Phosphonate Dimers: Dianions Supported by H-Bonds

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

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