6533b81ffe1ef96bd1277980

RESEARCH PRODUCT

A molecular electron density theory study of the chemo- and regioselective [3 + 2] cycloaddition reactions between trifluoroacetonitrile N-oxide and thioketones

Mar Ríos-gutiérrezLuis R. DomingoTian LuLeily Heidarpoor SaremiSaeedreza Emamian

subject

Electron density010405 organic chemistryChemistryGeneral Physics and AstronomyRegioselectivity010402 general chemistry01 natural sciencesElectron localization functionCycloaddition0104 chemical sciencesNucleophileComputational chemistryElectrophileReactivity (chemistry)Physical and Theoretical ChemistryBasis set

description

Abstract The [3 + 2] cycloaddition (32CA) reaction between trifluoroacetonitrile N-oxide (NO 7) and 2,2,4,4-tetramethyl-3-thioxocyclobutan-1-one (THK 12) as well as the self-dimerization of NO 7 as a competitive pathway were studied within the Molecular Electron Density Theory (MEDT) using several DFT functionals together with def2-TZVP basis set. Taking CCSD(T)/TZVP activation energies as reference, among the employed functionals, just the B2PLYP-D3(BJ) one is able to portray complete predominance of 32CA reaction over self-dimerization process in excellent agreement with the experimental outcomes. Analysis of the global reactivity indices permits to characterize NO 7 and THK 12 as a strong electrophile and a strong nucleophile, respectively, while analysis of the Parr functions allows explaining the chemo- and regioselectivity observed experimentally. The electron localization function (ELF) analysis of several points along the IRC profile associated with the energetically most favorable reaction channel permits to establish a non-concerted two-stage one-step molecular mechanism for this polar pmr-type 32CA reaction.

yearjournalcountryeditionlanguage
2018-02-01Chemical Physics
https://doi.org/10.1016/j.chemphys.2017.12.019