title: A theoretical study on diastereoselective oxidative dearomatization by iodoxybenzoic acid.
abstract: The reaction mechanism of diastereoselective oxidative dearomatization by iodoxybenzoic acid of key compounds involved in the total synthesis of epicocconone analogs, which are efficient fluorophores with a wide range of applications in protein staining and separation, was studied using density functional theory. In particular, the conformational space was investigated, as was the role of the so-called hypervalent twist move, which is thought to be the rate-determining step. Both kinetic and thermodynamical aspects of the mechanism were considered from static and dynamic viewpoints, including solvent effects. The results were then rationalized using conceptual density functional theory and Bader's atoms-in-molecules framework, which demonstrated how complementary these two approaches are when studying organic chemistry reactions theoretically.
authors.affiliation: Normandy Univ., COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesniére, 76821, Mont St Aignan, Cedex, France, vincent.tognetti@univ-rouen.fr.
authors.forename: Vincent
authors.initials: V
authors.lastname: Tognetti
authors.forename: Agathe
authors.initials: A
authors.lastname: Boulangé
authors.forename: Philippe A
authors.initials: PA
authors.lastname: Peixoto
authors.forename: Xavier
authors.initials: X
authors.lastname: Franck
authors.forename: Laurent
authors.initials: L
authors.lastname: Joubert
mesh_terms: D001578:Benzopyrans / Q000737:chemistry; D002412:Cations; D005663:Furans / Q000737:chemistry; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D007462:Iodobenzenes; D007463:Iodobenzoates / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D008962:Models, Theoretical; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D001578:Benzopyrans; D002412:Cations; D005663:Furans; D006841:Hydrocarbons, Aromatic; D007462:Iodobenzenes; D007463:Iodobenzoates; D007659:Ketones; C476101:o-iodoxybenzoic acid; C477464:epicocconone