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Arilación C-H catalizada por Ru de fluoroarenos con haluros de arilo

Marco Simonetti^1,2, Gregory J P Perry¹, Xacobe C Cambeiro¹

¹School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.

Journal of the American Chemical Society

|March 5, 2016

Resumen

Este estudio introduce la primera arilación C-H catalizada por rutenio de arenas sin grupos directos, lo que requiere inesperadamente ácido benzoico. La reacción

Área de la Ciencia:

Química orgánica
Química organometálica
Catálisis

Sus antecedentes:

La arilación C-H catalizada por rutenio de las arenas generalmente requiere grupos de dirección.
El logro de la arillación sin dirigir grupos presenta un desafío sintético significativo.

Objetivo del estudio:

Para informar de la primera arylación exitosa de C-H catalizada por rutenio de arenas en ausencia de grupos de dirección.
Aclarar el mecanismo y la regioselectividad de esta nueva transformación.

Principales métodos:

Catalización con rutenio
Estudios estoiquiométricos y mecanicistas de RMN
Experimentos de etiquetado de deuterio y efecto de isótopos cinéticos
Estudios computacionales

Principales resultados:

La arilación C-H de arenas que carecen de grupos directores se logró utilizando un catalizador de rutenio.
Se encontró que el ácido benzoico catalítico es esencial para que la reacción continúe.
La selectividad del sitio de arilación se rige por factores electrónicos y estéricos, que difieren de otros metales de transición.
Los estudios mecanicistas revelaron un catalizador Ru (II) libre de ligandos y una vía concertada de metalización-deprotonación (CMD).

Conclusiones:

Este trabajo amplía el alcance de la arilación C-H permitiendo la reacción sin dirigir grupos.
Los hallazgos ponen de relieve el papel único del ácido benzoico como aditivo en la catálisis del rutenio.
El estudio proporciona información fundamental sobre el mecanismo y la regioselectividad de la activación y arilación de C-H.

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