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Hidroxilación catalizada por cobre de haluros de (hetero) arilo bajo condiciones suaves

Shanghua Xia¹, Lu Gan¹, Kailiang Wang¹

¹Interdisciplinary Research Center on Biology and Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Lu, Shanghai 200032, China.

Journal of the American Chemical Society

|September 30, 2016

Resumen

Un nuevo sistema catalítico que utiliza el cobre (II) acetilacetonato (Cu) y el N,N'-bis (4-hidroxilo-2,6-dimetilfenilo) oxalamida (BHMPO) de manera eficiente para hidroxilar (hetero) haluros de arilo. Este método logra altos rendimientos para varios sustratos en condiciones suaves, ofreciendo un enfoque versátil para sintetizar fenoles y heteroarenos hidroxilados.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

La hidroxilación de haluros de (hetero) arilo es una transformación crucial en la síntesis orgánica.
El desarrollo de sistemas catalíticos eficientes y suaves sigue siendo un área activa de investigación.
Los catalizadores a base de cobre han demostrado ser prometedores en varias reacciones de acoplamiento cruzado.

Objetivo del estudio:

Desarrollar un nuevo y eficiente sistema catalítico para la hidroxilación de haluros de (hetero) arilo.
Investigar el alcance y las limitaciones del sistema catalítico desarrollado.
Para obtener altos rendimientos de fenoles y heteroarenos hidroxilados en condiciones de reacción suaves.

Principales métodos:

Se utilizó un sistema catalítico compuesto de cobre (II) acetilacetonato (Cu) y N,N'-bis (4-hidroxilo-2,6-dimetilfenilo) oxalamida (BHMPO).
Investigó la hidroxilación de una amplia gama de cloruros, bromuros y yoduros de (hetero) arilo.
Condiciones de reacción optimizadas, incluida la temperatura y la carga del catalizador.

Principales resultados:

Se han hidroxilado con éxito varios cloruros de (hetero) arilo, incluidos los que tienen grupos donantes o quitantes de electrones, a 130 °C, con rendimientos de buenos a excelentes.
Se ha conseguido una hidroxilación eficiente de los bromuros y yoduros de heteroarilo más reactivos a temperaturas más bajas (80 °C y 60 °C, respectivamente).
Se ha demostrado la eficacia del sistema catalítico a bajas cargas de cobre (0,5 mol % Cu).

Conclusiones:

La combinación de Cu ((acac) 2) y BHMPO representa un potente y versátil sistema catalítico para la hidroxilación del haluro de (hetero) arilo.
La metodología es eficaz para una amplia gama de sustratos, incluidos los cloruros difíciles.
El sistema funciona eficientemente en condiciones suaves y con bajas cargas de catalizador, lo que lo hace atractivo para aplicaciones sintéticas.

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