A molecular electron density theory study of the 3 + 2] cycloaddition reaction of nitrones with ketenes

Ríos-Gutiérrez, M. ; Darù, A. ; Tejero, T. (Universidad de Zaragoza) ; Domingo, L.R. ; Merino, P. (Universidad de Zaragoza)

Resumen: The 3 + 2] cycloaddition (32CA) reaction between nitrones and ketenes has been studied within the Molecular Electron Density Theory (MEDT) at the Density Functional Theory (DFT) MPWB1K/6-311G(d, p) computational level. Analysis of the conceptual DFT reactivity indices allows the explanation of the reactivity, and the chemo- and regioselectivity experimentally observed. The particular mechanism of this 32CA reaction involving low electrophilic ketenes has been elucidated by using a bonding evolution theory (BET) study. It is determined that this reaction takes place in one kinetic step only but in a non-concerted manner since two stages are clearly identified. Indeed, the formation of the second C-O bond begins when the first O-C bond is already formed. This study has also been applied to predict the reactivity of nitrones with highly electrophilic ketenes. Interestingly, this study predicts a switch to a two-step mechanism due to the higher polar character of this zw-type 32CA reaction. In both cases, BET supports the non-concerted nature of the 32CA reactions between nitrones and ketenes.

Idioma: Inglés

DOI: 10.1039/c6ob02768g

Año: 2017

Publicado en: ORGANIC & BIOMOLECULAR CHEMISTRY 15, 7 (2017), 1618-1627
ISSN: 1477-0520

Factor impacto JCR: 3.423 (2017)

Categ. JCR: CHEMISTRY, ORGANIC rank: 16 / 57 = 0.281 (2017) - Q2 - T1

Factor impacto SCIMAGO: 1.281 - Organic Chemistry (Q1) - Physical and Theoretical Chemistry (Q1) - Biochemistry (Q2)

Financiación: info:eu-repo/grantAgreement/ES/MINECO/BES-2014-068258
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-76155-R
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-78669-P

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Orgánica (Dpto. Química Orgánica)