Transient and intermediate carbocations in ruthenium tetroxide oxidation of saturated rings

Pedron, M. (Universidad de Zaragoza) ; Legnani, L. ; Chiacchio, M.A. ; Caramella, P. ; Tejero, T. (Universidad de Zaragoza) ; Merino, P. (Universidad de Zaragoza)

Resumen: The ruthenium tetroxide-mediated oxidation of cyclopentane, tetrahydrofuran, tetrahydrothiophene and N-substituted pyrrolidines has been studied computationally by DFT and topological (analysis of the electron localization function, ELF) methods. In agreement with experimental observations and previous DFT calculations, the rate-limiting step of the reaction takes place through a highly asynchronous (3 + 2) concerted cycloaddition through a single transition structure (one kinetic step). The ELF analysis identifies the reaction as a typical one-step-two-stages process and corroborates the existence of a transient carbocation. In the case of pyrrolidines, the carbocation is completely stabilized as an energy minimum in the form of an iminium ion and the reaction takes place in two steps.

Idioma: Inglés

DOI: 10.3762/bjoc.15.158

Año: 2019

Publicado en: BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY 15 (2019), 1552-1562
ISSN: 1860-5397

Factor impacto JCR: 2.622 (2019)

Categ. JCR: CHEMISTRY, ORGANIC rank: 23 / 57 = 0.404 (2019) - Q2 - T2

Factor impacto SCIMAGO: 0.714 - Organic Chemistry (Q2)

Financiación: info:eu-repo/grantAgreement/ES/DGA-FEDER/E34-R17
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-76155-R

Tipo y forma: Artículo (Versión definitiva)

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