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Oxidación remota de enlaces alifáticos C-H en moléculas que contienen nitrógeno

Jennifer M Howell¹, Kaibo Feng¹, Joseph R Clark¹

¹Roger Adams Laboratory, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois, 61801, United States.

Journal of the American Chemical Society

|November 5, 2015

Resumen

Este estudio introduce un nuevo método de complejación de nitrógeno para la oxidación remota de C-H en compuestos de aminas y piridina utilizando catalizadores de hierro. Este enfoque permite la funcionalización selectiva de moléculas previamente resistentes a tales transformaciones.

Área de la Ciencia:

Química orgánica
Catálisis
Química medicinal

Sus antecedentes:

Los heterociclos de nitrógeno son estructuras centrales en muchos productos farmacéuticos y naturales.
La funcionalización selectiva de los enlaces C-H sigue siendo un desafío importante en la síntesis orgánica.

Objetivo del estudio:

Desarrollar una nueva estrategia para la oxidación remota y no dirigida de C ((sp ((3)) -H de moléculas que contienen amina y piridina.
Explorar el uso de catalizadores de hierro sintonizables junto con la complejación de nitrógeno.

Principales métodos:

Utilizando una estrategia de complejación de nitrógeno con un ácido de Brønsted fuerte (HBF4) o un ácido de Lewis azofílico (BF3).
El uso de catalizadores de hierro sintonizables para lograr oxidaciones C ((sp ((3)) -H.
Investigación de la reactividad de los sustratos terciarios, secundarios y primarios que contienen aminas y piridinas.

Principales resultados:

Se han logrado con éxito oxidaciones remotas no dirigidas de C ((sp ((3)) -H.
Demostró la eficacia de la estrategia de complejación de nitrógeno con los ácidos de Brønsted y Lewis.
Identificó que las imidas resisten la oxidación y facilitan la funcionalidad remota.

Conclusiones:

La estrategia de complejación de nitrógeno desarrollada ofrece una herramienta poderosa para la funcionalización selectiva de compuestos que contienen nitrógeno.
Los catalizadores de hierro sintonizables, guiados por la complejación de nitrógeno, permiten una oxidación remota eficiente de C-H.
Este método expande la utilidad sintética de los derivados de aminas y piridina en el descubrimiento de fármacos y la síntesis de productos naturales.

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