6533b821fe1ef96bd127b8f9

RESEARCH PRODUCT

Unveiling the Different Reactivity of Bent and Linear Three-Atom-Components Participating in [3 + 2] Cycloaddition Reactions

Mar Ríos-gutiérrezFatemeh GhodsiLuis R. Domingo

subject

analytical_chemistry[3 + 2] cycloaddition reactionsOrganic chemistrychemical and pharmacologic phenomena010402 general chemistry01 natural sciencesQD241-441stomatognathic systemNucleophileComputational chemistrySingle bondReactivity (chemistry)skin and connective tissue diseasesCarbenoid010405 organic chemistryChemistrymolecular electron density theoryRegioselectivity16. Peace & justiceCycloaddition0104 chemical sciencesreactivitystomatognathic diseasesbent and linear three-atom-componentsregioselectivityElectrophileDensity functional theory

description

The reactivity of a series of pairs of bent and linear three-atom-component (B-TACs and L-TACs) participating in [3 + 2] cycloaddition (32CA) reactions towards ethylene and electrophilic dicyanoethylene (DCE) have been studied within the Molecular Electron Density Theory. While the pseudodiradical structure of B-TACs changes to that of pseudoradical or carbenoid L-TACs upon dehydrogenation, zwitterionic B-TACs remain unchanged. Conceptual Density Functional Theory (CDFT) indices characterize five of the nine TACs as strong nucleophiles participating in polar reactions towards electrophilic ethylenes. The activation energies of the 32CA reactions with electrophilic DCE range from 0.5 to 22.0 kcal·mol−1, being between 4.3 and 9.1 kcal·mol−1 lower than those with ethylene. In general, B-TACs are more reactive than their L-TAC counterparts. A change in the regioselectivity is found in these polar 32CA reactions

yearjournalcountryeditionlanguage
2021-08-13Organics
10.3390/org2030014http://dx.doi.org/10.3390/org2030014