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Diseño de un catalizador quiral plano de rodio-indenilo para la amidación alílica C-H regionalizada y

Caitlin M B Farr¹, Amaan M Kazerouni¹, Bohyun Park^2,3

¹Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.

Journal of the American Chemical Society

|July 16, 2020

Resumen

Los investigadores desarrollaron un nuevo complejo planar quiral de indenilo rodio para la funcionalización enantioselectiva de C-H. Este catalizador permite la amidación asimétrica C-H de las olefinas, produciendo valiosos productos enantioenriquecidos con alta selectividad.

Área de la Ciencia:

Química organometálica
Catálisis asimétrica
Funcionalidad C-H

Sus antecedentes:

Se sabe que los catalizadores Cp y Cp* del grupo IX producen reacciones enantioselectivas.
Las estrategias de enantiocontrol existentes se basan en el bloqueo estérico en el diseño del ligando.

Objetivo del estudio:

Desarrollar un nuevo complejo planar quiral de indenilo rodio para la funcionalización C-H enantioselectiva.
Explorar la asimetría electrónica en el diseño de ligandos para mejorar el enantiocontrol.

Principales métodos:

Síntesis de un nuevo complejo planar quiral de indenilo rodio.
Catalización de la amidación C-H alilica asimétrica con olefinas no activadas.
Estudios computacionales para elucidar los mecanismos de reacción.

Principales resultados:

El nuevo complejo cataliza eficientemente la amidación C-H alilica asimétrica.
Se obtuvieron altos rendimientos y una excelente regioselectividad y enantioselectividad para varios productos de amida alílica.
El análisis computacional indicó la escisión C-H como el paso determinante de la velocidad y la enantio.

Conclusiones:

El complejo de indenilo rodio desarrollado ofrece una nueva plataforma para la funcionalización enantioselectiva de C-H.
La asimetría electrónica en el diseño del ligando es una estrategia viable para controlar la enantioselectividad.
El catalizador proporciona acceso a amidas alilicas enriquecidas con enantio.

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