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Un acoplamiento radical general catalizado por cobre de haluros de alquilo no activados

Fu-Li Wang¹, Qian Xie², Xiao-Yu Chen²

¹College of Pharmacy, Shenzhen Technology University, Shenzhen 518118, China.

Journal of the American Chemical Society

|September 20, 2025

Resumen

Este estudio presenta un nuevo método de acoplamiento catalizado por cobre para haluros de alquilo no activados. El nuevo sistema amplía el alcance de la formación de enlaces C ((sp3) -N, lo que permite la funcionalización en etapa tardía de moléculas complejas.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

La catálisis de metales de transición de la primera fila es crucial para el acoplamiento cruzado C ((sp3)) -carbono/heteroatomo de haluros de alquilo no activados.
Los catalizadores de cobre se destacan en el acoplamiento cruzado C ((sp3) -N debido a su fácil eliminación reductora.
Existen limitaciones en la capacidad de reducción del cobre para sustratos desafiantes como los cloruros de alquilo.

Objetivo del estudio:

Desarrollar una reacción general de acoplamiento cruzado C(sp3)-C/N catalizada por cobre para haluros de alquilo no activados.
Para superar las limitaciones de los catalizadores de cobre en la activación de haluros de alquilo menos reactivos.
Para permitir la síntesis de diversos marcos moleculares a través de la funcionalidad en etapa tardía.

Principales métodos:

Se utilizan catalizadores de cobre con ligandos aniónicos N,N,N.
Se emplean condiciones térmicas suaves para las reacciones de acoplamiento cruzado.
Investigó el acoplamiento de varios haluros de alquilo (bromuros, cloruros, yoduros) con diversos nucleófilos.

Principales resultados:

Se ha conseguido el acoplamiento general C(sp3)-C/N catalizado por el cobre de haluros de alquilo no activados.
Se ha demostrado una mayor capacidad de reducción de los catalizadores Cu (I) utilizando ligandos aniónicos N,N,N.
Mostró un amplio alcance de sustrato que incluye haluros de alquilo primarios a terciarios y varios nucleófilos (aminas, indoles, amidas, alquinas).
Se ha confirmado la buena compatibilidad de los grupos funcionales y su aplicabilidad en la fase avanzada de la funcionalidad.

Conclusiones:

Desarrolló un protocolo versátil catalizado por cobre para el acoplamiento cruzado C-sp3.
El uso de ligandos aniónicos N,N,N es clave para mejorar el rendimiento del catalizador.
El método ofrece una poderosa plataforma para la síntesis de moléculas complejas y la funcionalización en etapa tardía.

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