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Aminación catalítica intermolecular C ((sp³) -H: Funcionalización selectiva de enlaces terciarios C-H frente a

Erwan Brunard¹, Vincent Boquet¹, Elsa Van Elslande¹

¹Université Paris-Saclay, CNRS, Institut de Chimie des Substances Naturelles, UPR 2301, 91198 Gif-sur-Yvette, France.

Journal of the American Chemical Society

|April 26, 2021

Resumen

Este estudio presenta un nuevo método catalítico para la funcionalización selectiva de enlaces terciarios C-H no activados. El robusto sistema basado en rodio produce eficientemente amidas α,α,α-trisubstituidas en condiciones suaves.

Área de la Ciencia:

Química orgánica
Catálisis
Funcionalidad C-H

Sus antecedentes:

Los enlaces terciarios C ((sp3)-H generalmente no son reactivos debido a sus altas energías de disociación de enlaces (BDE).
La funcionalización selectiva de estos enlaces sigue siendo un desafío importante en la química sintética.
Es muy deseable desarrollar métodos catalíticos para la aminación directa de tales enlaces inertes.

Objetivo del estudio:

Desarrollar un sistema catalítico para la aminación intermolecular selectiva del sitio de enlaces terciarios C ((sp3) -H no activados.
Para obtener altos rendimientos de amidas α,α,α-trisubstituidas.
Explorar el mecanismo de la selectividad del sitio en la funcionalidad C-H.

Principales métodos:

Se utilizó un complejo de rodio, Rh2S-tfpttl4, en combinación con sulfamato de tert-butilfenol (TBPhsNH2).
Se emplean condiciones oxidativas suaves para generar una especie discriminante de nitreno unida al rodio.
Se investigó la reacción en una escala de 50 mmol con una carga de catalizador baja (0,01 mol %).

Principales resultados:

Se ha logrado una aminación selectiva de enlaces terciarios C ((sp3) -H no activados (BDE 96 kcal·mol-1) por encima de los enlaces bencílicos C-H activados (BDE 85 kcal·mol-1).
Se obtienen amidas α,α,α-trisubstituidas en altos rendimientos.
Demostró la robustez y escalabilidad del sistema catalítico.
Se demostró que el grupo protector TBPhs puede eliminarse fácilmente para producir aminas libres.

Conclusiones:

Desarrolló un nuevo sistema catalítico para la aminación selectiva de enlaces terciarios C-H desafiantes.
El efecto sinérgico del catalizador de rodio y el reactivo de sulfamato es clave para la selectividad del sitio observada.
Este método ofrece una herramienta valiosa para sintetizar derivados de aminas complejas en condiciones suaves y eficientes.

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