Video Experimental Relacionado
Updated: May 8, 2026
10:10
Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes
Published on: July 28, 2018
Fosfonofluoración radical catalizada por plata de alquenos no activados
Chengwei Zhang1, Zhaodong Li, Lin Zhu
1Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, P.R. China.
Journal of the American Chemical Society
|September 13, 2013
Resumen
Este estudio introduce un nuevo método para la fosfonofluoración de alquenos utilizando la catálisis de nitrato de plata. El proceso crea eficientemente alquilfosfonatos fluorados con amplia aplicabilidad y buena estereoselectividad.
Área de la Ciencia:
- Química orgánica es la química orgánica.
- Química organometálica Química orgánica de los metales.
- Química del flúor Química del flúor
Sus antecedentes:
- Los alquenos no activados son sustratos difíciles para la funcionalización directa.
- El desarrollo de métodos catalíticos para la formación de enlaces C-P y C-F es crucial en la química sintética.
Objetivo del estudio:
- Desarrollar un método suave y catalítico para la fosfonofluoración de alquenos no activados.
- Para sintetizar alquilfosfonatos β-fluorados con alta eficiencia y estereoselectividad.
Principales métodos:
- Condensación catalítica de alquenos no activados con fosfito dietílico y Selectfluor.
- Utilizado el nitrato de plata (AgNO3) como catalizador en un sistema de disolventes CH2Cl2/H2O/HOAc a 40 °C.
Principales resultados:
- Se logró una síntesis eficiente de alquilfosfonatos β-fluorados.
- Se ha demostrado una buena estereoselectividad y una amplia compatibilidad de grupos funcionales.
- La reacción se lleva a cabo en condiciones suaves.
Conclusiones:
- Se ha establecido una nueva, leve y catalítica fosfonofluorización de alquenos no activados.
- El mecanismo propuesto implica pasos de transferencia de radicales catalizados por plata y átomos de flúor.
- Este método ofrece una herramienta valiosa para acceder a compuestos organofosforados fluorados complejos.
Videos de Conceptos Relacionados
01:17Radical Anti-Markovnikov Addition to Alkenes: Mechanism
The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy radical...
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy radical...
01:31Radical Substitution: Allylic Chlorination
Typically, when alkenes react with halogens at low temperatures, an addition reaction occurs. However, upon increasing the temperature or under reaction conditions that form radicals, providing a low but steady concentration of halogen radicals, allylic substitution reaction is favored. This is because allylic hydrogens are very reactive as the formed intermediate is resonance stabilized. For example, when propene is treated with chlorine in the gas phase at 400 °C, it undergoes allylic...
01:02Radical Reactivity: Electrophilic Radicals
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a low‐energy SOMO, which interacts...
01:27Radical Substitution: Halogenation of Alkanes and Alkyl Substituents
In the presence of heat or light, alkanes react with molecular halogens to form alkyl halides by a substitution reaction called radical halogenation. This reaction has three steps: initiation, propagation, and termination, as seen in the radical chlorination of methane to produce methyl chloride.
In the initiation step of the reaction, the chlorine molecule undergoes homolytic cleavage in the presence of light or heat, forming two highly reactive chlorine radicals. Propagation occurs in two...
In the initiation step of the reaction, the chlorine molecule undergoes homolytic cleavage in the presence of light or heat, forming two highly reactive chlorine radicals. Propagation occurs in two...
01:25Radical Anti-Markovnikov Addition to Alkenes: Overview
The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
01:16Radical Reactivity: Nucleophilic Radicals
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For instance, consider...