6533b7d6fe1ef96bd1265c1d

RESEARCH PRODUCT

Understanding the regioselectivity in hetero Diels–Alder reactions. An ELF analysis of the reaction between nitrosoethylene and 1-vinylpyrrolidine

Luis R. DomingoPatricia PérezJosé Antonio López Sáez

subject

Electron localization functionParameterChemistryOrganic ChemistryDensityRegioselectivityPhotochemistryCycloaddition reactionBiochemistryBond-formationElectron localization functionIndexIonNucleophileRadical ionReagentDrug DiscoveryElectrophileDiels alderQuantitative characterizationElectrophilicityTopological analysis13-Dipolar

description

[EN] The regioselectivity in the hetero Diels-Alder reaction between nitrosoethylene 1 and 1-vinylpyrrolidine 2 has been studied by a comparative ELF bonding analysis along the IRC of the endo/ortho and endo/meta regioisomeric channels at the B3LYP/6-31G*. level. Along the most favorable endo/ortho regioisomeric channel, the C-C sigma bond is first formed by coupling of two pseudoradical centers located at the most electrophilic carbon of 1 and the most nucleophilic center of 2. Formation of these relevant pseudoradical centers, which depend on the total charge transfer process along the polar reaction, and not on the approach mode of each reagent, is well characterized by analysis of the atomic spin density in the radical anion of nitrosoethylene 1 and in the radical cation of vinylpyrrolidine 2. (C) 2012 Elsevier Ltd. All rights reserved.

yearjournalcountryeditionlanguage
2013-01-07Tetrahedron
https://doi.org/10.1016/j.tet.2012.10.056