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La borilación por hidrogenación de alquenos permite una borilación catalizada por cobalto altamente activa y

Alex M Shimozono¹, Jose B Roque¹, Haozheng Li¹

¹Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.

Journal of the American Chemical Society

|July 18, 2025

Resumen

Este estudio introduce un nuevo método catalizado por cobalto para la borilación del areno C(sp2)-H, aumentando significativamente la actividad y logrando meta-selectividad con el tert-butileno. El proceso implica una secuencia de borilación-hidrogenación, lo que permite una eficiente funcionalización del areno.

Área de la Ciencia:

Química organometálica
Catálisis
Síntesis orgánica

Sus antecedentes:

La borilación C-H catalizada por cobalto es crucial para la funcionalización del areno.
El logro de una alta actividad y selectividad de sitio sigue siendo un desafío, especialmente para las arenas ricas en electrones.
Los métodos existentes a menudo luchan con el alcance del sustrato y la eficiencia de la reacción.

Objetivo del estudio:

Desarrollar un método de borilación del areno C ((sp2) -H catalizado por cobalto altamente activo y selectivo en el sitio.
Investigar el papel del tert-butileno (TBE) en la mejora de la actividad catalítica y la selectividad.
Para aclarar el mecanismo de reacción, incluido el origen de la meta-selectividad.

Principales métodos:

Reacciones de borilación catalizadas por cobalto utilizando varios arenes.
Monitoreo in situ de las reacciones catalíticas mediante espectroscopia de RMN de 1H.
Estudios sobre el efecto cinético de los isótopos y cálculos DFT para sondear el mecanismo de reacción.

Principales resultados:

La adición de tert-butileno (TBE) aumentó significativamente la actividad de la borilación catalizada por cobalto para las arenas ricas en electrones.
Se logró una alta meta-selectividad para los anisoles y anilinas monosubstituidos.
Se identificó una secuencia de borilación-hidrogenación de TBE como clave para mejorar la actividad, con la borilación del alqueno anterior a la funcionalización del areno.
Los efectos del isótopo cinético apoyaron la adición oxidativa irreversible y determinante del enlace C ((sp2) -H al cobalto ((I).

Conclusiones:

El método desarrollado proporciona una vía altamente activa y meta selectiva para la borilación del areno C ((sp2)) catalizado por cobalto.
El uso de TBE como aditivo es crucial para mejorar la actividad y superar los efectos inhibidores.
La adición oxidativa irreversible del enlace meta-C ((sp2) -H al cobalto ((I)) es el origen de la meta-selectividad observada.

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