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La hidroxilación C-H catalizada por rutenio en el ácido acuoso permite la funcionalización selectiva de derivados de

James B C Mack¹, John D Gipson², J Du Bois¹

¹Department of Chemistry, Stanford University , 337 Campus Drive, Stanford, California 94305, United States.

Journal of the American Chemical Society

|June 30, 2017

Resumen

Un nuevo método catalítico permite la hidroxilación selectiva de sp3 C-H en ácido acuoso, incluso para moléculas que contienen aminas. Este proceso catalizado por rutenio favorece la oxidación C-H sobre la oxidación N, ofreciendo una herramienta valiosa para la síntesis de moléculas complejas.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

La funcionalización selectiva de los enlaces C-H es un desafío clave en la síntesis orgánica.
La oxidación de sustratos que contienen aminas a menudo conduce a reacciones secundarias de N-oxidación no deseadas.
El desarrollo de sistemas catalíticos que funcionen en medios acuosos es deseable para la sostenibilidad.

Objetivo del estudio:

Identificar, optimizar y evaluar un nuevo protocolo catalítico para la hidroxilación sp3 C-H.
Desarrollar un método para la oxidación de sustratos con grupos funcionales de aminas básicas.
Investigar la selectividad y el resultado estereoquímico de la reacción de hidroxilación.

Principales métodos:

Se utilizó un catalizador de bis (bipiridina) rutenio (Ru) en condiciones acuosas ácidas.
Se ha probado una gama de derivados de aminas y sustratos derivados de terpenos.
Se han realizado estudios cinéticos preliminares para evaluar la estabilidad y la reactividad del catalizador.

Principales resultados:

Se ha logrado una hidroxilación selectiva terciaria y bencílica sp3 C-H, superando la oxidación N para sustratos de aminas.
Se observaron tendencias similares de reactividad con sustratos derivados de terpenos.
Se ha demostrado la hidroxilación enantiospecífica de los centros quirales terciarios a pesar de la fuerza ionizante del medio de reacción.
La cinética preliminar indicó la estabilidad de configuración de los catalizadores cis- y trans-Ru.

Conclusiones:

El protocolo desarrollado catalizado por Ru proporciona un método selectivo para la hidroxilación sp3 C-H de compuestos que contienen aminas en ácido acuoso.
El método muestra un amplio alcance del sustrato y un alto control estereoquímico.
La estabilidad y la selectividad del catalizador ofrecen potencial para la síntesis de moléculas complejas y el descubrimiento de fármacos.

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