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Una estrategia fotocatalítica general para la aminación nucleofílica de enlaces bencílicos C-H primarios y

Madeline E Ruos¹, R Garrison Kinney^1,2, Oliver T Ring^1,3

¹Department of Chemistry and Biochemistry, University of California-Los Angeles, Los Angeles, California 90095, United States.

Journal of the American Chemical Society

|August 11, 2023

Resumen

Un nuevo método de luz visible permite la aminación de enlaces C-H utilizando nuevos precursores de radicales y fotocatalizadores. Este enfoque crea eficientemente diversos enlaces C ((sp3) -N para aplicaciones farmacéuticas.

Área de la Ciencia:

Química orgánica
Fotocatálisis
Metodología sintética

Sus antecedentes:

La funcionalización del enlace C ((sp3) -H es crucial para la síntesis de moléculas complejas.
El desarrollo de métodos suaves y eficientes para la formación de enlaces C-N sigue siendo un desafío.

Objetivo del estudio:

Desarrollar un método catalizado por fotorreducción de luz visible para la aminación nucleofílica de enlaces bencílicos C ((sp3) -H.
Establecer un protocolo modular y libre de metales para la construcción de enlaces C ((sp3) -N farmacéuticamente relevantes.

Principales métodos:

Utilizando un nuevo precursor de radical amidil y un fotocatalizador orgánico bajo irradiación de luz visible.
Empleando una transferencia secuencial de átomos de hidrógeno (HAT) y un mecanismo de cruce oxidativo radical-polar.
Interceptando el carbocatión generado con varios nucleófilos centrados en N.

Principales resultados:

Aminación exitosa de los enlaces bencílicos primarios y secundarios C ((sp3) -H.
Amplio alcance del sustrato que incluye nitriles, amidas, carbamatos, sulfonamidas y azoles.
Condiciones de reacción unificadas para diversas construcciones de enlaces C ((sp3) -N.

Conclusiones:

El método desarrollado ofrece un enfoque suave, libre de metales y modular para la diversificación de enlaces C ((sp3) -H.
El protocolo permite la síntesis rápida de productos aminados relevantes para la química farmacéutica.
Los estudios mecanicistas confirmaron la HAT mediada por el radical amidil y la vía de apagado reductivo del fotocatalizador.

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