Catalytic Effect of Electric Fields on the Kemp Elimination Reactions with Neutral Bases

Carles Acosta‐Silva, Joan Bertran, Vicenç Branchadell, Antoni Oliva

Research output: Contribution to journalArticleResearchpeer-review

Abstract

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.

Original languageEnglish
Pages (from-to)2594-2604
Number of pages11
JournalChemPhysChem
Volume21
Issue number22
DOIs
Publication statusPublished - 23 Oct 2020

Keywords

  • Kemp elimination reaction
  • enzymes
  • external oriented fields
  • solvent model based on density (SMD)
  • solvent reaction field
  • DESIGN
  • BENZISOXAZOLES
  • NONCOVALENT INTERACTIONS
  • PHYSICAL ORGANIC-CHEMISTRY
  • DENSITY FUNCTIONALS
  • ORIGIN
  • ENZYMES
  • SYSTEMS
  • OPTIMIZATION
  • ELECTROSTATIC CATALYSIS

Fingerprint

Dive into the research topics of 'Catalytic Effect of Electric Fields on the Kemp Elimination Reactions with Neutral Bases'. Together they form a unique fingerprint.

Cite this