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RESEARCH PRODUCT
A Molecular Electron Density Theory Study of the Reactivity of Azomethine Imine in [3+2] Cycloaddition Reactions
Luis R. DomingoMar Ríos-gutiérrezsubject
Models MolecularThiosemicarbazones[3+2] cycloaddition reactionsImineMolecular Conformationmolecular mechanismsazomethine iminePharmaceutical ScienceElectronsElectronic structureActivation energy010402 general chemistry01 natural sciencesArticlebonding evolution theoryAnalytical Chemistrychemistry.chemical_compoundNucleophileComputational chemistryDrug Discoveryconceptual density functional theoryMoleculeReactivity (chemistry)organic_chemistryelectron densityPhysical and Theoretical Chemistryazomethine imine; [3+2] cycloaddition reactions; molecular electron density theory; conceptual density functional theory; electron localisation function; bonding evolution theory; electron density; molecular mechanisms; chemical reactivityCycloaddition ReactionMolecular Structure010405 organic chemistrymolecular electron density theoryOrganic ChemistryCycloaddition0104 chemical scienceschemistryChemistry (miscellaneous)ElectrophileQuantum TheoryThermodynamicsMolecular MedicineDensity functional theoryImineselectron localisation functionAzo Compoundschemical reactivitydescription
The electronic structure and the participation of the simplest azomethine imine (AI) in [3+2] cycloaddition (32CA) reactions have been analysed within the Molecular Electron Density Theory (MEDT) using DFT calculations at the MPWB1K/6-311G(d) level. Electron localisation function (ELF) topological analysis reveals that AI has a pseudoradical structure, while the conceptual DFT reactivity indices characterise this TAC as a moderate electrophile and a good nucleophile. The non-polar 32CA reaction of AI with ethylene takes place through a one-step mechanism with low activation energy, 5.3 kcal/mol-1. A bonding evolution theory (BET) study indicates that this reaction takes place through a non-concerted [2n+2τ] mechanism in which the C–C bond formation is clearly anticipated prior to the C–N one. On the other hand, the polar 32CA reaction of AI with dicyanoethylene takes place through a two-stage one-step mechanism. Now, the more favourable regioisomeric transition state structure (TS) is located 8.5 kcal•mol−1 below the reagents, in complete agreement with the high polar character of the TS. The current MEDT study makes it possible to extend Domingo’s classification of 32CA reactions to a new pra-type of reactivity.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2017-05-06 | Molecules; Volume 22; Issue 5; Pages: 750 |