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Relaciones estructura-reactividad de las fosfinas de tipo Buchwald en acoplamientos cruzados catalizados por níquel

Samuel H Newman-Stonebraker^1,2, Jason Y Wang^1,2, Philip D Jeffrey³

¹Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.

Journal of the American Chemical Society

|October 17, 2022

Resumen

Los ligandos de fosfina de tipo Buchwald se destacan en las reacciones de acoplamiento cruzado catalizadas por níquel como el acoplamiento Suzuki Miyaura. Este estudio revela sus relaciones estructura-reactividad, allanando el camino para una nueva química de níquel orgánico.

Área de la Ciencia:

Química organometálica
Catálisis
Química sintética

Sus antecedentes:

Las fosfinas dialquilo-orto-biarilas (ligandos de tipo Buchwald) son cruciales en el acoplamiento cruzado catalizado por el paladio.
Su aplicación en el acoplamiento catalizado por níquel está creciendo, mostrando un alto rendimiento en el acoplamiento Suzuki Miyaura (SMC) y el acoplamiento C-N.
Existe una comprensión limitada con respecto a las relaciones estructura-reactividad (SRR) de estos ligandos con níquel.

Objetivo del estudio:

Para analizar las relaciones estructura-reactividad (SRR) de los ligandos de fosfina de tipo Buchwald en reacciones de acoplamiento cruzado catalizadas por níquel.
Proporcionar una comprensión mecanicista del acoplamiento cruzado catalizado por níquel utilizando ligandos de tipo Buchwald.
Establecer una base para futuras investigaciones en química orgánica de níquel y nuevas metodologías de acoplamiento cruzado.

Principales métodos:

Investigó las SRR de fosfina de tipo Buchwald en cuatro reacciones distintas de acoplamiento cruzado catalizadas por níquel.
Se utilizó un análisis de clasificación basado en datos para orientar el estudio.
Se han llevado a cabo estudios organometálicos mecanicistas en los que se han caracterizado estructuralmente los complejos Ni{0}, Ni{1} y Ni{2}.

Principales resultados:

Los ligandos de tipo Buchwald demuestran un rendimiento superior en el acoplamiento Suzuki Miyaura catalizado por níquel (SMC) y el acoplamiento C-N, a menudo superando a las bisfosfinas tradicionales.
Modelos de reactividad racionalizados en catálisis a través de estudios mecanicistas y análisis de datos.
Proporcionó información sobre el comportamiento de complejos de níquel bien definidos con ligandos de tipo Buchwald.

Conclusiones:

Este estudio aclara las relaciones estructura-reactividad de los ligandos de fosfina de tipo Buchwald en la catálisis del níquel.
Los hallazgos ofrecen una plataforma para el avance de la química de níquel orgánico.
Esta investigación facilita el desarrollo de nuevos métodos de acoplamiento cruzado catalizado por níquel.

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