Por favor, use este identificador para citar o enlazar este ítem:https://uvadoc.uva.es/handle/10324/65052
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-VCH
Documento Fuente
Adv. Synth. Catal. 2021, 363, 4795 – 4804
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 (normalizadas)
Química
Materias Unesco
23 Química
Palabras Clave
C-H activation
olefination
palladium
Catalysis
metal-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 León-FEDER; Grant VA224P20
Ministerio de Educación; FPU-17/04559 fellowship
Junta de Castilla y León-FEDER; Grant VA224P20
Ministerio de Educación; FPU-17/04559 fellowship
Version del Editor
Idioma
spa
Tipo de versión
info:eu-repo/semantics/publishedVersion
Derechos
openAccess
Aparece en las colecciones
Arquivos deste item
Tamaño:
5.692Mb
Formato:
Adobe PDF
Descripción:
Artículo
![Attribution-NonCommercial-NoDerivatives 4.0 Internacional](/themes/Mirage2//images/creativecommons/cc-by-nc-nd.png)