6533b85afe1ef96bd12ba046
RESEARCH PRODUCT
An MEDT study of the carbenoid-type [3 + 2] cycloaddition reactions of nitrile ylides with electron-deficient chiral oxazolidinones.
Luis R. DomingoPatricia PérezMar Ríos-gutiérrezsubject
chemistry.chemical_classificationElectron densityNitrile010405 organic chemistryStereochemistryOrganic ChemistryActivation energy010402 general chemistry01 natural sciencesBiochemistryCycloaddition0104 chemical scienceschemistry.chemical_compoundchemistryNucleophileElectrophilePhysical and Theoretical ChemistryCarbenoidNitrile ylidedescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2016-10-19 | Organicbiomolecular chemistry |