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Migración de arilo a arilo de 1,3-rodío dirigida por metoxí

Jing Zhang¹, Jun-Feng Liu, Angel Ugrinov

¹Department of Chemistry and Biochemistry, North Dakota State University , Fargo, North Dakota 58102, United States.

Journal of the American Chemical Society

|November 1, 2013

Resumen

Este estudio detalla una migración única de 1,3-rodío en un complejo Rh(I), que permite la formación de enlaces C-C meta-selectivos a través de la adición de conjugado descarboxilativo y la activación de C-H.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
La catálisis es la catálisis.
Síntesis orgánica La síntesis orgánica.

Sus antecedentes:

El desplazamiento metal/hidrógeno a través del espacio es una estrategia clave en la activación de enlaces C-H catalizados por metales de transición.
Los complejos de rodio (I) son catalizadores ampliamente utilizados en las transformaciones orgánicas.

Objetivo del estudio:

Para sintetizar y caracterizar un complejo Rh (I) 2,6-dimetoxibenzoato.
Para investigar el mecanismo de una nueva migración de 1,3-rodio.
Explorar la aplicación de esta migración en reacciones catalizadas por Rh (I).

Principales métodos:

Síntesis y caracterización de un complejo Rh (I).
Estudios de reordenamiento estequiométrico.
Adición de conjugado descarboxilativo catalizado por Rh (I). adición conjugada descarboxilativa catalizada por Rh (I).
Estudios de etiquetado de deuterio.

Principales resultados:

Se sintetizó y caracterizó el complejo A Rh(I) 2,6-dimetoxibenzoato.
Se observó una migración muy inusual de 1,3-rodio (cambio de arilo a arilo de 1,3-Rh/H).
Este cambio permitió la formación de enlaces C-C meta-selectivos en una adición conjugada descarboxilativa.
El etiquetado de deuterio reveló la participación del grupo orto-metoxi en la activación de C-H durante la protodecarboxilación.

Conclusiones:

El estudio demuestra una nueva vía de migración de 1,3-rodio.
Esta vía ofrece una nueva estrategia para la funcionalización meta-selectiva a través de la activación de C-H.
Los hallazgos amplían el alcance de las reacciones catalizadas por rodio y las metodologías de activación de C-H.

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