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Acoplamiento descarbonizado Suzuki-Miyaura de fluoruros ácidos sin bases y catalizado por níquel

Christian A Malapit¹, James R Bour¹, Conor E Brigham¹

¹Department of Chemistry, University of Michigan, Ann Arbor, MI, USA.

|October 26, 2018

Resumen

Este estudio introduce una nueva reacción catalizada por níquel que acopla eficientemente los ácidos borónicos con los fluoruros ácidos, eliminando la necesidad de bases externas. Este avance amplía el alcance del acoplamiento cruzado Suzuki-Miyaura para sustratos sensibles a las bases.

Área de la Ciencia:

Química orgánica
Catálisis
Química medicinal

Sus antecedentes:

El acoplamiento cruzado Suzuki-Miyaura es vital para la formación de enlaces C-C, pero normalmente requiere bases.
Las bases exógenas pueden degradar sustratos orgánicos sensibles, limitando el alcance de la reacción.
Las estrategias anteriores se centraron en reactivos enmascarados o catalizadores altamente activos para superar los problemas mediados por bases.

Objetivo del estudio:

Desarrollar una reacción de acoplamiento cruzado tipo Suzuki-Miyaura sin bases.
Identificar una combinación catalizador-electrófilo que permita reacciones sin bases exógenas.
Ampliar la utilidad del acoplamiento cruzado para moléculas sensibles a las bases y biológicamente relevantes.

Principales métodos:

Desarrolló un acoplamiento catalizado por níquel de ácidos aril borónicos con fluoruros ácidos.
Fluoruros ácidos generados in situ a partir de ácidos carboxílicos fácilmente disponibles.
Se utiliza una vía mecanicista que incluye un intermediario de fluoruro de níquel arilo "activo para la transmetalización".

Principales resultados:

Logrado acoplamiento tipo Suzuki-Miyaura sin la necesidad de una base exógena.
Aplicabilidad demostrada a una amplia gama de ácidos borónicos sensibles a las bases.
Acoplamiento exitoso de ácidos carboxílicos biológicamente activos a través de sus fluoruros ácidos generados in situ.

Conclusiones:

El nuevo método catalizado por níquel ofrece una alternativa libre de bases para el acoplamiento cruzado Suzuki-Miyaura.
Este enfoque evita los problemas de descomposición del sustrato asociados con las reacciones tradicionales mediadas por bases.
La metodología amplía las posibilidades sintéticas en química orgánica y medicinal.

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