Video Experimental Relacionado

Updated: Sep 4, 2025

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Published on: May 21, 2019

Trifluorometilación radical enantioselectiva de enlaces bencílicos C-H mediante fotorreducción cooperativa y

Pin Xu¹, Wenzheng Fan¹, Pinhong Chen¹

¹State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

Journal of the American Chemical Society

|July 21, 2022

Resumen

Este estudio introduce la primera trifluorometilación radical enantioselectiva de enlaces bencílicos C-H mediante fotorreducción cooperativa y catálisis de cobre. Este método proporciona un acceso eficiente a diversos productos trifluorometilados con alta enantioselectividad en condiciones suaves.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

Los enlaces bencílicos C-H son frecuentes en productos farmacéuticos y materiales orgánicos.
La trifluorometilación enantioselectiva es crucial para la introducción de grupos que contienen fluor.
Los métodos existentes para la trifluorometilación bencílica a menudo carecen de enantiocontrol o requieren condiciones severas.

Objetivo del estudio:

Desarrollar la primera trifluorometilación radical enantioselectiva de enlaces bencílicos C-H.
Establecer un sistema cooperativo de fotorreducción y catálisis de cobre para esta transformación.
Proporcionar un método suave y eficiente para acceder a los compuestos quirales bencílicos trifluorometilados.

Principales métodos:

Utilizó un sistema cooperativo de fotorreducción y catálisis de cobre.
Se utiliza un proceso de transferencia de átomos de hidrógeno (HAT) para la generación de radicales bencílicos a partir de arenas alquilo a través de la catálisis fotorredóxica.
Catálisis de cobre apalancado para la trifluorometilación enantioselectiva de los radicales bencílicos generados.

Principales resultados:

Logró la primera trifluorometilación radical enantioselectiva de enlaces bencílicos C-H.
Se ha demostrado el acceso directo a productos de trifluorometilación bencílica estructuralmente diversos.
Se obtienen buenos rendimientos con enantioselectividades excelentes en condiciones de reacción suaves.
Mostró un amplio alcance de sustrato y una excelente compatibilidad de grupo funcional.

Conclusiones:

El sistema cooperativo de fotorreducción y catálisis de cobre desarrollado es esencial para la trifluorometilación bencílica enantioselectiva.
Este método ofrece un avance significativo en la síntesis de compuestos trifluorometilados quirales.
El protocolo proporciona una vía versátil y eficiente para acceder a valiosas moléculas orgánicas fluoradas.

Más Videos Relacionados

Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes

Application of Elemental Lanthanides in the Selective C-F Activation of Trifluoromethylated Benzofulvenes Providing Access to Various Difluoroalkenes

Published on: July 28, 2018

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Published on: January 19, 2016

Videos de Conceptos Relacionados

Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene

Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene

Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.

Reactions at the Benzylic Position: Halogenation

Reactions at the Benzylic Position: Halogenation

Benzylic halogenation takes place under conditions that favor radical reactions such as heat, light, or a free radical initiator like peroxide.

Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism

Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism

Birch reduction uses solvated electrons as reducing agents. The reaction converts benzene to 1,4-cyclohexadiene. The reaction proceeds by the transfer of a single electron to the ring to form a benzene radical anion. This anion is highly basic—it abstracts a proton from the alcohol to form a cyclohexadienyl radical. Another single electron transfer gives the cyclohexadienyl anion. A proton transfer from the alcohol forms 1,4-cyclohexadiene. Since this reduction occurs via radical anion...

Reactions at the Benzylic Position: Oxidation and Reduction

Reactions at the Benzylic Position: Oxidation and Reduction

The benzylic position describes the position of a carbon atom attached directly to a benzene ring. Benzene by itself does not undergo oxidation. In contrast, the benzylic carbon is quite reactive in the presence of strong oxidizing agents such as KMnO4 or H2CrO4. Therefore, alkylbenzenes are readily oxidized to benzoic acid, irrespective of the type of alkyl groups.

Nucleophilic Aromatic Substitution: Elimination–Addition

Nucleophilic Aromatic Substitution: Elimination–Addition

Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...