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Catalytic Effect of Electric Fields on the Kemp Elimination Reactions with Neutral Bases
Author(s) -
AcostaSilva Carles,
Bertran Joan,
Branchadell Vicenç,
Oliva Antoni
Publication year - 2020
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000667
Subject(s) - electric field , catalysis , methylamine , chemistry , solvent , acetonitrile , reaction rate , chemical reaction , solvent effects , chemical physics , computational chemistry , photochemistry , organic chemistry , physics , quantum mechanics
The effect of solvent reaction fields and oriented electric fields on the Kemp elimination reaction between methylamine or imidazole and 5‐nitrobenzisoxazole has been theoretically studied. The Kemp reaction is the most widely used for the design of new enzymes. Our results, using the SMD continuous model for solvents, are in quite good agreement with the experimental fact that the rate of the analogous reaction with butylamine is one order of magnitude smaller in water than in acetonitrile. In the case of external electric fields, our results show that they can increase or decrease the energy barrier depending on the magnitude and orientation of the field. A duly oriented electric field may have a notable catalytic effect on the reaction. So, external electric fields and reaction fields due to the medium can contribute to the design of new enzymes. Several factors that must be taken into account to increase the catalytic effect are discussed.