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Arilación selectiva en etapa tardía de las trialquilaminas habilitada por la catálisis dual de Ni/Fotoredox

Yangyang Shen¹, Tomislav Rovis¹

¹Department of Chemistry, Columbia University, New York, New York 10027, United States.

Journal of the American Chemical Society

|September 30, 2021

Resumen

Un nuevo método de doble catálisis níquel/fotorredóxido permite la α-arilación selectiva de las triquilaminas. Este enfoque proporciona una vía versátil para sintetizar estructuras de aminas complejas, incluso en modificaciones farmacéuticas de última etapa.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

Las trialquilaminas son bloques de construcción versátiles para la síntesis de aminas complejas.
El desarrollo de métodos selectivos para la funcionalización de aminas es crucial en la química orgánica.
Los métodos existentes para la arilación de aminas a menudo carecen de selectividad del sitio o requieren condiciones duras.

Objetivo del estudio:

Desarrollar un nuevo sistema catalítico para la α-arilación selectiva del sitio de las triquilaminas.
Demostrar la amplia aplicabilidad del método en varios sustratos de triquilamina.
Para investigar la vía mecanicista de la reacción catalítica.

Principales métodos:

Utilizó un sistema de doble catálisis de níquel y fotorreducción.
Utilizó una amplia gama de trialquilaminas, incluidas las que se encuentran en compuestos farmacéuticos.
Realizó estudios mecanicistas para comprender el comportamiento del catalizador y la intercepción radical.

Principales resultados:

Se ha logrado una selectividad N-Me exclusiva en la α-arilación de diversas triquilaminas.
Se ha demostrado la eficacia del método en condiciones de reacción leve.
Se ha demostrado la arilación exitosa en etapa tardía de compuestos farmacéuticos que contienen el motivo N-metilo.
Los estudios mecanicistas revelaron que solo los radicales α-amino primarios sufren acoplamiento cruzado.

Conclusiones:

La estrategia de doble catálisis níquel/fotorredóxido desarrollada ofrece una herramienta poderosa para la α-arilación selectiva del sitio de las triquilaminas.
Este método proporciona un acceso eficiente a arquitecturas de aminas complejas con alta selectividad.
Los hallazgos tienen implicaciones significativas para el descubrimiento y desarrollo de fármacos a través de la funcionalización en etapa tardía.

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