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Un acoplamiento enantioselectivo Suzuki-Miyaura para formar bifenolos axialmente quirales

Robert Pearce-Higgins¹, Larissa N Hogenhout¹, Philip J Docherty¹

¹Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.

Journal of the American Chemical Society

|August 15, 2022

Resumen

Los investigadores desarrollaron un nuevo método para crear bifenolos enriquecidos con enantio utilizando un ligando de SPhos sulfonado modificado (sSPhos). Este avance en la catálisis atroposelectiva ofrece un enfoque práctico para sintetizar valiosas moléculas quirales.

Área de la Ciencia:

Química orgánica
Catálisis asimétrica
Moléculas quirales

Sus antecedentes:

La quiralidad axial es crucial en las moléculas biológicamente relevantes y en el diseño del catalizador quiral.
Los atropisómeros 2,2'-bifenol son frecuentes en estas áreas.
Los métodos de acoplamiento atroposelectivo catalizado por metales existentes tienen limitaciones para acceder directamente a los bifenolos enriquecidos con enantio.

Objetivo del estudio:

Para abordar el desafío de sintetizar directamente bifenolos enriquecidos con enantio.
Explorar el uso de un nuevo ligando de SPhos (sSPhos) enantiopuro y sulfonado para la catálisis atroposelectiva.
Investigar el mecanismo detrás de la inducción asimétrica en el acoplamiento Suzuki-Miyaura utilizando sSPhos.

Principales métodos:

Utilizado enantiopuro, ligando de SPhos sulfonado (sSPhos) en las reacciones de acoplamiento Suzuki-Miyaura.
Introducción de la quiralidad en el ligando SPhos mediante sulfonación para crear el eje atropisomérico.
Desarrolló un método práctico de resolución para sSPhos utilizando la recristalización de sales diastereoméricas.

Principales resultados:

Se han obtenido altos niveles de inducción asimétrica en los productos de 2,2'-bifenol.
Demostró la eficacia del ligando sSPhos sulfonado en el acoplamiento atroposelectivo Suzuki-Miyaura.
Resolvió con éxito el ligando sSPhos, permitiendo su uso en forma enantiopura.

Conclusiones:

Las interacciones no covalentes atractivas que involucran al grupo sulfonato del ligando sSPhos son clave para una alta inducción asimétrica.
El método desarrollado proporciona una vía práctica para obtener bifenolos enriquecidos con enantio.
Este trabajo amplía la utilidad de los ligandos SPhos en la catálisis asimétrica.

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