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Estudios mecanicistas de la reacción de aminación directa C-H catalizada por rodio utilizando azidas como fuente de

Sae Hume Park¹, Jaesung Kwak, Kwangmin Shin

¹Center for Catalytic Hydrocarbon Functionalizations, Institute of Basic Science (IBS) , Daejeon 305-701, Republic of Korea.

Journal of the American Chemical Society

|January 24, 2014

Resumen

Este estudio detalla el mecanismo de aminación directa C-H catalizada por Rh utilizando azidas orgánicas. Se prefiere una vía escalonada que implique un intermediario Rh(V) -nitrenoide sobre la formación concertada de enlaces C-N, siendo la formación de nitrenoides la que limita la velocidad.

Área de la Ciencia:

Química orgánica es la química orgánica.
La catálisis es la catálisis.
Mecanismos de reacción Mecanismos de reacción

Sus antecedentes:

La aminación directa C-H proporciona una ruta fácil a las anilinas, evitando los haluros de arilo.
La aminación C-H mediada por metales ha avanzado significativamente en alcance y condiciones.

Objetivo del estudio:

Para dilucidar los detalles mecánicos de la aminación directa de C-H catalizada por Rh utilizando azidas orgánicas.
Para investigar las etapas clave de la formación de nitrenoides metálicos, la inserción y la regeneración del catalizador.

Principales métodos:

Cálculos de la Teoría Funcional de la Densidad (DFT).
Estudios cinéticos. estudios de la cinética.
Investigación de los intermediarios del ciclo catalítico.

Principales resultados:

Se prefiere una vía escalonada que involucre un intermediario Rh ((V) -nitrenoide.
La inserción de amido en un intermediario de rhodacycle es un paso clave.
La formación intermedia de nitrenoides, no la activación C-H, es el paso que limita la velocidad.

Conclusiones:

El mecanismo involucra aspectos tanto de la esfera interna como de la externa.
Comprender el mecanismo ayuda a optimizar las reacciones directas de aminación C-H.
Este trabajo aclara el papel de las especies de Rh-nitrenoides en la funcionalización C-H.

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