title: An MEDT study of the carbenoid-type [3 + 2] cycloaddition reactions of nitrile ylides with electron-deficient chiral oxazolidinones.
abstract: The molecular mechanism of the carbenoid-type [3 + 2] cycloaddition (32CA) reactions of a nitrile ylide (NY) with a non-chiral and a chiral oxazolidinone has been studied within Molecular Electron Density Theory (MEDT) at the MPWB1K/6-31G(d) computational level. Topological analysis of the Electron Localisation Function (ELF) of the NY shows that it presents a carbenoid structure. The high nucleophilic character of the NY together with the electrophilic character of the non-chiral oxazolidinone favour a polar 32CA reaction with a very low activation energy, the reaction being completely meta/endo selective. A Bonding Evolution Theory (BET) study of the molecular mechanism makes it possible to characterise a two-stage one-step carbenoid-type mechanism. Non-Covalent Interactions (NCI) analysis of the 32CA reaction between the NY and chiral oxazolidinone correctly explains the diastereoselectivity experimentally observed.
authors.affiliation: Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, E-46100 Burjassot, Valencia, Spain. domingo@utopia.uv.es.
authors.forename: Luis R
authors.identifier: http://orcid.org/0000-0002-2023-0108
authors.initials: LR
authors.lastname: Domingo
authors.affiliation: Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, E-46100 Burjassot, Valencia, Spain. domingo@utopia.uv.es.
authors.forename: Mar
authors.initials: M
authors.lastname: Ríos-Gutiérrez
authors.affiliation: Universidad Andres Bello, Facultad de Ciencias Exactas, Departamento de Ciencias Químicas, Millennium Nucleus Chemical Processes and Catalysis (CPC), Av. República 498, 8370146, Santiago, Chile. p.perez@unab.cl.
authors.forename: Patricia
authors.initials: P
authors.lastname: Pérez