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Síntesis y acoplamiento cruzado Suzuki-Miyaura de alquilaminoboranos. Una estrategia habilitada por los radicales

Cornelia S Buettner¹, Chiara Stavagna¹, Michael J Tilby²

¹Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany.

Journal of the American Chemical Society

|August 13, 2024

Resumen

Este estudio introduce un nuevo método para sintetizar compuestos orgánicos alquilo estables utilizando radicales de boro. Estos nuevos materiales son efectivos en las reacciones de acoplamiento cruzado Suzuki-Miyaura, ofreciendo una alternativa a los métodos tradicionales.

Área de la Ciencia:

Química orgánica
Química organometálica

Sus antecedentes:

Los organoborones alquilo son reactivos clave para la formación de enlaces carbono-carbono, principalmente a través del acoplamiento cruzado Suzuki-Miyaura.
Los métodos actuales a menudo se basan en procesos de 2 electrones, lo que limita el alcance y la estabilidad de las especies de organoboron accesibles.

Objetivo del estudio:

Desarrollar una estrategia alternativa de borilación utilizando radicales de boro ligados a aminas.
Para sintetizar nuevos organoboron alifáticos estables, incluidos los derivados α-amino difíciles.
Para demostrar la utilidad de estos nuevos compuestos en las reacciones de acoplamiento cruzado Suzuki-Miyaura.

Principales métodos:

Oxidación fotorredóxica y descarboxilación de boranos ligados a aminas para generar radicales de borilo.
Adición radical de radicales de borilo a los estirenos y las iminas a través del cruce radical-polar.
Aplicación directa de organoboros sintetizados en el acoplamiento cruzado Suzuki-Miyaura con haluros de arilo.

Principales resultados:

Se sintetizó una nueva clase de organoborones alifáticos sólidos estables, resistentes a la protodeboronación.
Se prepararon con éxito nuevos derivados de α-amino organoboron sin protección.
Estos organoborones participaron eficientemente en el acoplamiento cruzado Suzuki-Miyaura con haluros de arilo complejos.
Los hallazgos preliminares indican la posibilidad de liberación lenta de ácidos alquilo borónicos difíciles de manejar.

Conclusiones:

La estrategia de borilación por fotorreducción desarrollada proporciona acceso a organoborones alifáticos estables.
Estos nuevos organoborones expanden la utilidad del acoplamiento cruzado Suzuki-Miyaura para la síntesis de moléculas complejas.
El método ofrece una alternativa estable para el almacenamiento y la utilización de especies reactivas de alquilo boro.

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