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Funcionalización atroposelectiva y diversa a través de la resolución cinética

Jian-Jun Li¹, Xiao-Xuan Zeng¹, Xin Kuang¹

¹State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, CAS 345 Lingling Road, Shanghai 200032, P. R. China.

Journal of the American Chemical Society

|February 14, 2025

Resumen

Este estudio introduce un nuevo método para crear moléculas quirales con andamios de biarilo metafuncionalizados utilizando catálisis de paladio y resolución cinética. Este avance permite la síntesis de atropisómeros complejos para productos farmacéuticos y ciencia de los materiales.

Área de la Ciencia:

Química orgánica
Catálisis
Síntesis asimétrica

Sus antecedentes:

Los andamios de biarilo quiral son cruciales en productos farmacéuticos y ligandos.
La funcionalización atroposelectiva en la meta-posición de los biarilos es un desafío.

Objetivo del estudio:

Desarrollar un nuevo método para la funcionalización atroposelectiva meta-C-H.
Para sintetizar los productos de biarilo meta-funcionalizados enriquecidos con enantio, en particular los derivados de la quinolina.

Principales métodos:

Se utiliza la activación enantioselectiva de C-H catalizada por el paladio.
Se empleó un ligando de aminoácido monoprotectado quiral (MPAA) y un mediador de norborneno transitorio racémica.
Reacción iniciada con la activación orto-C-H enantioselectiva a través de la resolución cinética, seguida por un relé Catellani.

Principales resultados:

Logró una atroposelectiva y remota funcionalización meta-C-H.
Sintetizó diversos atropisómeros basados en quinolina enriquecidos con enantio con alta estereoselectividad (factores S hasta 458).
Se ha demostrado una metaalqueinilación y alquinilación enantioselectiva sin precedentes.

Conclusiones:

El método desarrollado proporciona un acceso eficiente a valiosos andamios de biarilo quirales metafuncionalizados.
Los compuestos sintetizados tienen aplicaciones potenciales en productos farmacéuticos, ligandos quirales y materiales funcionales.
Utilidad sintética demostrada mediante la creación de nuevos ligandos P, N y materiales quirales con actividad CPL.

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