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Estereodivergente controlada por ligandos para la α-vinilización y la α-arilación de las columnas vertebrales de

Jie Hu¹, Shengjie Su¹, Haodong Zhang¹

¹Center for Supramolecular Chemistry and Catalysis, College of Sciences, Shanghai University, 99 Shang-Da Road, Shanghai 200444, China.

Journal of the American Chemical Society

|October 8, 2025

Resumen

Este estudio introduce un nuevo método para modificar las columnas vertebrales de péptidos utilizando el acoplamiento cruzado catalizado por níquel. Este enfoque permite la funcionalización estereoselectiva en sitios internos, superando un obstáculo sintético significativo en la química de los péptidos.

Área de la Ciencia:

Química orgánica
Química sintética
Química de los péptidos

Sus antecedentes:

La modificación estereoselectiva de los α-carbonos de la columna vertebral del péptido en los sitios internos es un desafío sintético significativo.
El acoplamiento cruzado C-C catalizado por metales de transición no se ha aplicado previamente a este problema.

Objetivo del estudio:

Desarrollar un nuevo método para la modificación estereoselectiva de los α-carbonos de la columna vertebral interna del péptido.
Para utilizar el acoplamiento cruzado C-C catalizado por metales de transición para la funcionalización de la columna vertebral del péptido.

Principales métodos:

Se instaló una unidad de α-C-tosil glicinilo (TsG) dentro de la columna vertebral del péptido.
Las reacciones de vinilación y arilación reductora catalizadas por níquel se realizaron utilizando triflados o haluros de vinilo y arilo.
La quiralidad del ligando se ajustó para controlar la estereoselectividad.

Principales resultados:

La unidad TsG sirvió como un electrofilo eficaz para el acoplamiento cruzado C-C catalizado por Ni.
Los péptidos modificados por α-C ((sp²) fueron sintetizados con alta diastereoselectividad.
La modificación estereodivergente en los sitios internos del péptido se logró mediante el control de la quiralidad del ligando.

Conclusiones:

Este estudio presenta un avance en la modificación de la columna vertebral de péptidos en etapa tardía utilizando estrategias de acoplamiento cruzado.
El método desarrollado ofrece un raro ejemplo de control estereodivergente en sitios internos de la columna vertebral del péptido.
Se espera que los hallazgos estimulen una mayor investigación en la funcionalización de péptidos.

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