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Sustitución aromática nucleofílica de fluoroarenos no activados habilitada por catálisis fotorredóxica orgánica

Vincent A Pistritto¹, Megan E Schutzbach-Horton¹, David A Nicewicz¹

¹Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States.

Journal of the American Chemical Society

|September 28, 2020

Resumen

Este estudio introduce un nuevo método para la sustitución aromática nucleofílica (S_NAr) en fluoroarenos no activados mediante catálisis fotorredóxica. Este enfoque expande las reacciones S_NAr a sustratos neutros y ricos en electrones, lo que permite la funcionalización en etapa tardía.

Área de la Ciencia:

Química orgánica
Química sintética
Fotocatálisis

Sus antecedentes:

La sustitución aromática nucleofílica (S_NAr) tradicionalmente requiere fluoroarenos pobres en electrones.
Las fluoroarenas neutras en electrones y ricas en electrones son sustratos desafiantes para el S_NAr.
Existe la necesidad de una aplicabilidad más amplia de S_NAr, especialmente para moléculas complejas.

Objetivo del estudio:

Desarrollar un nuevo método para la desfluorización nucleofílica de fluoroarenos no activados.
Para permitir las reacciones de S_NAr en fluoroarenas neutras y ricas en electrones.
Demostrar la utilidad de este método en la funcionalización tardía de los productos farmacéuticos.

Principales métodos:

Utilizando la catálisis fotorredóxica orgánica para generar radicales catiónicos reactivos.
El uso de condiciones de reacción suaves para la simplicidad operativa.
Investigando una gama de nucleófilos que incluyen azoles, aminas y ácidos carboxílicos.

Principales resultados:

Desfluorización nucleofílica exitosa de fluoroarenos no activados.
Se ha demostrado una amplia gama de compatibilidad nucleofílica.
Aplicación a la funcionalización de determinados heterociclos fluorados y compuestos farmacéuticos.
Los estudios computacionales confirmaron la selectividad del sitio regida por la electrónica de arenas.

Conclusiones:

El método S_NAr acelerado por radicales catiónicos desarrollado amplía el alcance de la sustitución aromática nucleofílica.
Este enfoque catalizado por fotorreducción ofrece una herramienta suave y versátil para sintetizar fluoroarenos funcionalizados.
El método es particularmente valioso para la funcionalización en etapas tardías en el descubrimiento y desarrollo de fármacos.

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