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La borilación dirigida por cloruro de arilo C (sp2) -H habilitada por la catálisis del iridio

Hongliang Zhao^1,2, Chao-Yue Zhao³, Lili Chen¹

¹State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.

Journal of the American Chemical Society

|November 7, 2023

Resumen

Este estudio introduce un método catalizado por iridio para la borilación C-H enantioselectiva de cloruros de arilo, creando diversos biarilos axialmente quirales con alta selectividad. El sistema catalítico eficiente logró un número récord de volumen de negocios (TON) para la activación asimétrica de C-H.

Área de la Ciencia:

Química organometálica
Catálisis asimétrica
Química orgánica sintética

Sus antecedentes:

Los cloruros de arilo son bloques de construcción sintéticos importantes.
El desarrollo de métodos eficientes para crear moléculas quirales es crucial en la síntesis orgánica.
La activación asimétrica C-H ofrece una ruta directa a las estructuras quirales complejas.

Objetivo del estudio:

Desarrollar una borilación C-H enantioselectiva catalizada por iridio de cloruros de arilo.
Para sintetizar una amplia gama de biarilos axialmente quirales con alta enantioselectividad.
Para lograr un alto número de volumen de negocios (TON) en la activación asimétrica de C-H dirigida por el grupo funcional.

Principales métodos:

Reacción de borilación C-H catalizada por iridio.
Utilizando compuestos biarílicos procirales como sustratos.
Emplear un catalizador con una quiralidad incompatible con el sustrato.

Principales resultados:

Se logró una borilación C-H enantioselectiva exitosa de cloruros de arilo.
Se sintetizó una biblioteca diversa de biarilos axialmente quirales con altas enantioselectividades.
Se obtuvo un número de facturación récord (TON) de 7000, atribuido a la interacción débil entre catalizador y sustrato.
Utilidad sintética demostrada a través de la funcionalización de enlaces C-B, ortho-C-H y C-Cl.

Conclusiones:

El método desarrollado catalizado por iridio es muy eficaz para sintetizar biarilos quirales axialmente.
El alto TON destaca la eficiencia y el potencial de este sistema catalítico para la activación asimétrica de C-H.
El método proporciona una plataforma versátil para la construcción de poliarenos quirales complejos.

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