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Adición oxidativa y hidrofuncionalización de enlaces C-C σ mediante un complejo de diironio soportado por un

Tianchang Liu¹, Ryan P Murphy¹, Patrick J Carroll¹

¹Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.

Journal of the American Chemical Society

|July 26, 2022

Resumen

Este estudio demuestra nuevas reacciones de adición oxidativa no asistida para la activación de enlaces C-C utilizando un complejo de diironio. Estos hallazgos permiten una eficiente funcionalización de enlaces C-C a través de ciclos catalíticos.

Área de la Ciencia:

Química organometálica
Catálisis
Química sintética

Sus antecedentes:

La activación del enlace C-C es crucial para la síntesis orgánica.
El desarrollo de nuevos métodos catalíticos para la funcionalización de los enlaces C-C sigue siendo un desafío importante.

Objetivo del estudio:

Informar los primeros ejemplos de reacciones de adición oxidativa sin ayuda de enlaces C ((sp) -C ((sp2) y C ((sp) -C ((sp3).
Para explorar los ciclos catalíticos para la funcionalidad del enlace sigma C-C.

Principales métodos:

Utilizando un complejo de diironio, (3PDI2) Fe2 ((μ-N2) ((PPh3) 2 ([Fe2N]), para las reacciones de adición oxidativa.
Reaccionando [Fe2N] con varios difenilacetilenos y derivados de la fenilalquina.
Investigar las reacciones de hidrofuncionalización posteriores con H2 o HBpin.

Principales resultados:

Se obtiene adición oxidativa sin ayuda de enlaces C(sp) -C(sp2) con difenilacetilenos.
Se ha observado la activación selectiva de enlaces C ((sp) -C ((sp2) o C ((sp) -C ((sp3) con fenilalquinas basándose en la impedancia estérica.
Se ha demostrado la hidrofuncionalización catalítica (hidrogenación e hidroboración) de los enlaces C-C sigma, regenerando el complejo de diirón.

Conclusiones:

El complejo de diirón facilita reacciones de adición oxidativa de enlaces C-C sin precedentes.
Este trabajo proporciona una nueva vía catalítica para la funcionalización del enlace sigma C-C, ofreciendo productos termodinámicamente favorables.

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