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Título: | Deoxygenation of Oxiranes by ¿3¿3-Phosphorus Reagents ¿ Computational Mechanistic and Stereochemical Study |
Fecha de publicación: | 17-oct-2023 |
Editorial: | Wiley-VCH Gmb |
Cita bibliográfica: | ChemPlusChem 2024, 89, e202300474 (1 of 9) |
ISSN: | Electronic: 2192-6506 |
Palabras clave: | DFT calculations Deoxygenation Oxiranes Carbene transfer Pnictogens |
Resumen: | The deoxygenation of parent and substituted oxiranes by λ3 σ3 - phosphorus reagents has been explored in detail, therefore unveiling mechanistic aspects as well as regio- and stereochemical consequences. Attack to a ring C atom is almost always preferred over one-step deoxygenation by direct P-to-O attack. In most cases a carbene transfer occurs as first step, leading to a phosphorane and a carbonyl unit that thereafter react in the usual Wittig fashion via the corresponding λ5 σ5 -1,2- oxaphosphetane intermediate. Betaines rarely constitute true minima after the first C-attack to oxiranes, at least in the gasphase. Use of the heavier derivatives AsMe3 and SbMe3 as oxirane deoxygenating reagents was also mechanistically studied. The thermodynamic tendency of λ3 σ3 -phosphorus reagents to act as oxygen (O-attack) or carbene acceptors (Cattack) was theoretically studied by means of the thermodynamic oxygen-transfer potential (TOP) and the newly defined thermodynamic carbene-transfer potential (TCP) parameters, that were explored in a wider context together with many other acceptor centres. |
Autor/es principal/es: | Espinosa Ferao, Arturo Francisco |
Facultad/Departamentos/Servicios: | Facultades, Departamentos, Servicios y Escuelas::Departamentos de la UMU::Química Orgánica |
Forma parte de: | Part of a Special Collection: “From Light to Heavy: Advancing the Chemistry of Pnictogen Compounds" |
URI: | http://hdl.handle.net/10201/141929 |
DOI: | https://doi.org/org/10.1002/cplu.2023004 |
Tipo de documento: | info:eu-repo/semantics/article |
Número páginas / Extensión: | 9 |
Derechos: | info:eu-repo/semantics/openAccess Attribution-NonCommercial-NoDerivatives 4.0 Internacional |
Descripción: | ©2023 The Author. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/. This document is the Published version of a published Work that appeared in final form in ChemPlusChem. To access the final edited and published work see https://doi.org/org/10.1002/cplu.2023004 |
Aparece en las colecciones: | Artículos: Química Orgánica |
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