title: External electric field will control the selectivity of enzymatic-like bond activations.
abstract: Controlling the selectivity of a chemical reaction is a Holy Grail in chemistry. This paper reports theoretical results of unprecedented effects induced by moderately strong electric fields on the selectivity of two competing nonpolar bond activation processes, C-H hydroxylation vs C=C epoxidation, promoted by an active species that is common to heme-enzymes and to metallo-organic catalysts. The molecular system by itself shows no selectivity whatsoever. However, the presence of an electric field induces absolute selectivity that can be controlled at will. Thus, the choice of the orientation and direction of the field vis-à-vis the molecular axes drives the reaction in the direction of complete C-H hydroxylation or complete C=C epoxidation.
authors.affiliation: Contribution from the Department of Organic Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, the Hebrew University of Jerusalem, 91904 Jerusalem, Israel.
authors.forename: Sason
authors.initials: S
authors.lastname: Shaik
authors.forename: Sam P
authors.initials: SP
authors.lastname: de Visser
authors.forename: Devesh
authors.initials: D
authors.lastname: Kumar
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D004560:Electricity; D004798:Enzymes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry; D006420:Hemeproteins / Q000737:chemistry*; D006900:Hydroxylation; D013816:Thermodynamics
chemical_list: D004798:Enzymes; D004852:Epoxy Compounds; D006420:Hemeproteins