Identificador persistente para citar o vincular este elemento: http://hdl.handle.net/10553/75157
Título: Theoretical study of the mutarotation of erythrose and threose: acid catalysis
Autores/as: Azofra Mesa, Luis Miguel 
Alkorta, Ibon
Elguero, José
Clasificación UNESCO: 2307 Química física
Palabras clave: Hemiacetal reaction
DFT-calculations
Lewis acid
Hard-Pearson acid
Brønsted acid, et al.
Fecha de publicación: 2013
Publicación seriada: Carbohydrate Research 
Resumen: The acid catalysis of the mutarotation mechanism in the two aldotetroses,D-erythrose andD-threose, hasbeen studied at B3LYP/6-311++G(d,p) computational level in gas phase and in solution employing thePCM–water model. The open-chain, the furanose and the connecting TS structures have been character-ized. To study the enhancing effect of acid groups on the electrophilicity of the carbonyl carbon atom, foursituations have been considered: (i) a classical Lewis acid as BH3; (ii) a classical hard-Pearson acid as Na+;(iii) classical Brønsted acids as H+and H3O+; and (iv) a combined strategy using H3O+and one bridge-H2Omolecule as assistant in the proton transfer process. All the acidic groups reduce the activation energywith exception of the Na+, which can act, in some cases, as inhibitor. It is greatly reduced by the presenceof Brønsted acids (iii) and through the combined strategy (iv). For this last mechanism, the electronic acti-vation energies are between 12 and 43 kJ mol 1in vacuum and between 13 and 25 kJ mol 1in watersolution, through the use of the PCM model.
URI: http://hdl.handle.net/10553/75157
ISSN: 0008-6215
DOI: 10.1016/j.carres.2013.01.013
Fuente: Carbohydrate research [ISSN 0008-6215], v. 372, p.1-8
Colección:Artículos
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