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Catálisis de relés de Cu/Ir para la borilación de alquenos regionales y enantioselectivos/alquilación allílica

Wen-Bin Cao¹, Hui Xu¹, Yi-Zhe Lou¹

¹New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.

Journal of the American Chemical Society

|July 14, 2025

Resumen

Este estudio introduce una nueva catálisis de relevos de cobre/iridio para crear moléculas complejas con una estereocímica precisa. El método sintetiza eficientemente compuestos quirales con alta selectividad, lo que permite el acceso a todos los estereoisómeros.

Área de la Ciencia:

Química orgánica
Catálisis
Síntesis estereoselectiva

Sus antecedentes:

La creación de moléculas con múltiples estereocentros es difícil.
Las reacciones asimétricas de sustitución alelica son clave para esto.
Los métodos anteriores tenían limitaciones en cuanto a selectividad y alcance.

Objetivo del estudio:

Desarrollar un nuevo sistema catalítico para la síntesis estereoselectiva.
Para utilizar reactivos de alquilcobre en la sustitución asimétrica de alelo.
Para lograr un alto control de la regioselectividad, la diastereoselectividad y la enantioselectividad.

Principales métodos:

Se empleó la catálisis por relés de Cu/Ir.
Los reactivos de alquilcobre se generaron in situ mediante la difuncionalización borilativa mediada por Cu de los estirenos.
Estos nucleófilos reaccionaron con los electrófilos π-alilo-Ir derivados de los carbonatos de alilo.

Principales resultados:

Se obtuvieron altos rendimientos (hasta el 90%).
Se observó una excelente regioselectividad (> 20:1 dr) y una enantioselectividad (> 99% ee).
Los cuatro estereoisómeros posibles fueron sintetizados selectivamente ajustando las configuraciones de los ligandos.

Conclusiones:

La catálisis del relé Cu/Ir es muy eficaz para la síntesis estereoselectiva.
Este método proporciona acceso a diversas moléculas quirales.
La reacción demuestra una utilidad sintética significativa y el potencial para futuras aplicaciones.

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