Por favor, use este identificador para citar o enlazar este ítem:https://uvadoc.uva.es/handle/10324/49029
Título
Non‐chelate‐assisted palladium‐catalyzed aerobic oxidative heck reaction of fluorobenzenes and other arenes: When does the C−H activation need help?
Año del Documento
2021
Editorial
Wiley
Descripción
Producción Científica
Documento Fuente
Advanced Synthesis & Catalysis, 2021, vol. 363, p. 1-11
Resumo
The pyridone fragment in the ligand [2, 2’-bipyridin]-6(1H)-one (bipy-6-OH) enables the oxidative Heck reaction of simple arenes with oxygen as the sole oxidant and no redox mediator. Arenes with either electron-donating or electron-withdrawing groups can be functionalized in this way. Experimental data on the reaction with toluene as the model arene shows that the C−H activation step is turnover limiting and that the ligand structure is crucial to facilitate the reaction, which supports the involvement of the pyridone fragment in the C−H activation step. In the case of fluoroarenes, the alkenylation of mono and 1,2-difluoro benzenes requires the presence of bipy-6-OH. In contrast, this ligand is detrimental for the alkenylation of 1,3-difluoro, tri, tetra and pentafluoro benzenes which can be carried out using just [Pd(OAc)2]. This correlates with the acidity of the fluoroarenes, the most acidic undergoing easier C−H activation so other steps of the reaction such as the coordination-insertion of the olefin become kinetically important for polyfluorinated arenes. The use of just a catalytic amount of sodium molybdate as a base proved to be optimal in all these reactions.
Materias Unesco
23 Química
22 Física
Palabras Clave
Activación C-H
Olefination
Palladium
Ligand cooperation
Oxygen
ISSN
1615-4150
Revisión por pares
SI
Patrocinador
Ministerio de Ciencia e Innovación (AEI, grant PID2019-111406GB-I00)
Junta de Castilla y Leoń-FEDER (grant VA224P20)
Ministerio de Educación y Formación Profesional (fellowship FPU-17/04559)
Junta de Castilla y Leoń-FEDER (grant VA224P20)
Ministerio de Educación y Formación Profesional (fellowship FPU-17/04559)
Version del Editor
Propietario de los Derechos
© 2021 The Authors
Idioma
eng
Tipo de versión
info:eu-repo/semantics/publishedVersion
Derechos
openAccess
Aparece en las colecciones
Arquivos deste item
![Attribution-NonCommercial-NoDerivatives 4.0 Internacional](/themes/Mirage2//images/creativecommons/cc-by-nc-nd.png)