title: Modeling the mechanism of glycosylation reactions between ethanol, 1,2-ethanediol and methoxymethanol.
abstract: The mechanism of the S(N)2 model glycosylation reaction between ethanol, 1,2-ethanediol and methoxymethanol has been studied theoretically at the B3LYP/6-311+G(d,p) computational level. Three different types of reactions have been explored: (i) the exchange of hydroxyl groups between these model systems; (ii) the basic catalysis reactions by combination of the substrates as glycosyl donors (neutral species) and acceptors (enolate species); and (iii) the effect on the reaction profile of an explicit H2O molecule in the reactions considered in (ii). The reaction force, the electronic chemical potential and the reaction electronic flux have been characterized for the reaction path in each case. Energy calculations show that methoxymethanol is the worst glycosyl donor model among the ones studied here, while 1,2-ethanediol is the best, having the lowest activation barrier of 74.7 kJ mol(-1) for the reaction between this one and the ethanolate as the glycosyl acceptor model. In general, the presence of direct interactions between the atoms involved in the penta-coordinated TS increases the activation energies of the processes.
authors.affiliation: Instituto de Química Médica, IQM-CSIC, Madrid, Spain. luisazofra@iqm.csic.es
authors.forename: Luis Miguel
authors.initials: LM
authors.lastname: Azofra
authors.forename: Ibon
authors.initials: I
authors.lastname: Alkorta
authors.forename: Alejandro
authors.initials: A
authors.lastname: Toro-Labbé
authors.forename: José
authors.initials: J
authors.lastname: Elguero
mesh_terms: D002384:Catalysis; D000431:Ethanol / Q000737:chemistry*; D019855:Ethylene Glycol / Q000737:chemistry*; D006031:Glycosylation; D000432:Methanol / Q000031:analogs & derivatives / Q000737:chemistry*; D008958:Models, Molecular; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D014867:Water; D000431:Ethanol; D019855:Ethylene Glycol; D000432:Methanol