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Ipso-borilación de éteres de arilo a través de una hendidura de C-OMe catalizada por Ni

Cayetana Zarate¹, Rubén Manzano¹, Ruben Martin^1,2

¹†Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain.

Journal of the American Chemical Society

|May 16, 2015

Resumen

Este estudio introduce una nueva borilación catalizada por níquel de éteres de arilo, que escinden eficientemente los enlaces carbono-oxígeno. La reacción ofrece selectividad de sitio ajustable, lo que permite diversas aplicaciones sintéticas.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
Química orgánica sintética y orgánica.

Sus antecedentes:

Los éteres de arilo son motivos estructurales prevalentes en productos farmacéuticos y materiales.
Los métodos eficientes para la funcionalización de éteres de arilo, particularmente a través de la escisión de enlaces C-O, son muy buscados.
Los métodos de borilación existentes a menudo carecen de la capacidad de dirigirse selectivamente a diferentes enlaces C-O dentro de la misma molécula.

Objetivo del estudio:

Desarrollar un nuevo método catalizado por níquel para la ipso-borilación de éteres de arilo.
Para lograr la escisión selectiva de cualquiera de los enlaces arilo C(sp2)-OMe o alquilo C(sp3)-OMe.
Para demostrar la amplia aplicabilidad y la selectividad ajustable de la reacción de borilación desarrollada.

Principales métodos:

Reacción de acoplamiento cruzado catalizada por níquel.
Utilizó varios éteres de arilo como sustratos.
Se emplearon diferentes reactivos de boro para controlar la selectividad del sitio.
Optimización de las condiciones de reacción, incluyendo la carga del catalizador, la temperatura y el disolvente.

Principales resultados:

Se logró con éxito la ipso-borilación de éteres de arilo a través de la escisión de enlaces C(sp2)-OMe y C(sp3)-OMe.
La reacción exhibe un amplio alcance de sustrato, tolerando diversos grupos funcionales.
Se ha demostrado una exquisita selectividad del sitio que se puede controlar fácilmente mediante la elección del reactivo de boro.
Se emplearon condiciones de reacción leve, mejorando la practicidad del método.

Conclusiones:

Desarrolló una versátil ipso-borilación catalizada por Ni de éteres de arilo.
El método proporciona una poderosa herramienta para la funcionalización selectiva de enlaces C-O.
La capacidad de cambiar la selectividad del sitio ofrece ventajas significativas para la síntesis de moléculas complejas.

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