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Síntesis asimétrica de naftolos y naftilaminas remotamente quirales a través de los metidos de nafthoquinona

Shuxuan Liu^1,2,3, Ka Lok Chan¹, Zhenyang Lin¹

¹Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology (HKUST), Clear Water Bay, Kowloon 999077, Hong Kong SAR, China.

Journal of the American Chemical Society

|June 5, 2023

Resumen

Este estudio introduce un nuevo método de síntesis asimétrica que utiliza metidas de quinona extendidas, lo que permite la creación eficiente de compuestos aromáticos quirales. Estos nuevos métodos permiten el acceso a naftos y naftilaminas valiosas de alta enantioselectividad.

Área de la Ciencia:

Química orgánica
Síntesis asimétrica
Catálisis

Sus antecedentes:

Los metidos de quinona son intermediarios cruciales en la síntesis asimétrica.
Los metidos de quinona extendida, con unidades de carbonio y metido separadas, siguen siendo poco explorados para aplicaciones asimétricas.

Objetivo del estudio:

Desarrollar el primer protocolo de síntesis asimétrica utilizando intermedios extendidos de metido de quinona.
Establecer un método suave de una sola olla para generar compuestos aromáticos remotamente quirales.

Principales métodos:

Generación in situ de 2-naftoquinona 8-metidos y aza-análogos mediante el uso de ácidos fosfóricos quirales.
Reacciones de adición nucleófilas asimétricas.
Cálculos de la Teoría Funcional de la Densidad (DFT) para elucidar los mecanismos de reacción.

Principales resultados:

Desarrollo exitoso de un nuevo proceso asimétrico para las metidas extendidas de quinona.
Síntesis eficiente y altamente enantioselectiva de diversos naftos y naftilaminas.
Conocimientos mecánicos que sugieren un doble papel para los catalizadores de ácido fosfórico en el estado de transición.

Conclusiones:

Este trabajo es pionero en el uso de metidas de quinona extendidas como intermedios versátiles en síntesis asimétrica.
Se establece una nueva plataforma sintética para la construcción de centros estereogénicos bencílicos remotos en sistemas aromáticos.
Los hallazgos abren vías para acceder a moléculas quirales anteriormente desafiantes.

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