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Acoplamiento C-N descarboxilador sp3 mediante catálisis doble de cobre y fotorredóxido

Yufan Liang¹, Xiaheng Zhang¹, David W C MacMillan²

¹Merck Center for Catalysis at Princeton University, Princeton, NJ, USA.

|June 22, 2018

Resumen

Este estudio introduce un nuevo método de catálisis de cobre y fotorredóxido para la creación de enlaces carbono-nitrógeno sp3. Este eficiente sistema de acoplamiento cruzado utiliza ácidos carboxílicos disponibles y diversos nucleófilos de nitrógeno.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

Se han logrado avances significativos en la formación de enlaces carbono-nitrógeno (C-N) sp2 a través de la catálisis de metales de transición (palladio, cobre, níquel).
La formación de enlaces sp3 C-N utilizando sustratos alquilo sigue siendo un desafío persistente en la química de acoplamiento cruzado.

Objetivo del estudio:

Desarrollar un método general y eficaz para la construcción de enlaces sp3 C-N.
Para abordar el desafío de incorporar sustratos alquilo en la formación de enlaces C-N.

Principales métodos:

Combinación sinérgica de catálisis de cobre y catálisis fotorredóxica.
Utiliza ácidos alquilcarboxílicos (primario, secundario, terciario a través de la activación de yodo) como fuentes de alquilo.
Emplea una amplia gama de nucleófilos de nitrógeno, incluidos los heterociclos, las amidas, las sulfonamidas y las anilinas.

Principales resultados:

Se consigue un acoplamiento C-N eficiente a temperatura ambiente en tiempos de reacción cortos (de 5 minutos a 1 hora).
Se ha demostrado una amplia aplicabilidad en varios ácidos alquilo-carboxílicos y nucleófilos de nitrógeno.
Demostró una alta regioselectividad con sustratos de poliamina y una funcionalización exitosa en etapa tardía de moléculas complejas de fármacos.

Conclusiones:

El sistema catalítico desarrollado proporciona una plataforma versátil para sintetizar productos N-alquilo.
Permite la construcción rápida de la complejidad molecular y la funcionalización en etapa tardía de los productos farmacéuticos.
Ofrece un avance significativo para abordar el desafío de la formación de enlaces sp3 C-N.

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