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Regioselectividad inusual en la hidrogenación heterogénea catalizada por Pd de derivados de naftaleno funcionalizados

Qingduan Meng^1,2, Wei Hao^1,2, Gaoyuan Zhang^1,2

¹Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.

Journal of the American Chemical Society

|November 6, 2025

Resumen

Este estudio introduce un nuevo método de hidrogenación catalizado por el paladio para los derivados de naftaleno sustituidos por P^V. El proceso logra una alta regioselectividad, lo que permite una síntesis eficiente de valiosos compuestos de tetrahidronaftaleno.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

La hidrogenación regioselectiva de los derivados de naftaleno, especialmente el anillo funcionalizado, es un desafío significativo en la síntesis orgánica.
El desarrollo de métodos eficientes y selectivos para reducir los anillos aromáticos en moléculas complejas es crucial para acceder a nuevas estructuras químicas.

Objetivo del estudio:

Informar sobre la primera hidrogenación heterogénea catalizada por el paladio de derivados de naftaleno sustituidos por P^V.
Para lograr una alta regioselectividad en la reducción del anillo aromático funcionalizado.
Para demostrar la utilidad sintética de este método en la preparación de valiosos ligandos.

Principales métodos:

Se utilizó un catalizador Pd/Al₂O₃ comercialmente disponible y reciclable para la hidrogenación heterogénea.
Se ha investigado la regioselectividad de la hidrogenación de los óxidos de naftalen-1-ilfosfina y de los óxidos de naftalen-2-ilfosfina.
Se han realizado estudios mecanicistas para elucidar la vía de reacción.

Principales resultados:

Se obtiene una alta regioselectividad (hasta > 95:5 rr) y rendimiento (hasta 99%) en la hidrogenación de óxidos de naftalen-1-ilfosfina a óxidos de 1,2,3,4-tetrahidronaftalen-1-ilfosfina.
Se observó una reversión en la regioselectividad al cambiar el grupo P^V a la posición C2, dando 5,6,7,8-tetrahidronaftalen-2-il óxidos de fosfina.
Se han sintetizado con éxito nuevos ligandos quirales P,N y H₈ de tipo Cy-BINAP.

Conclusiones:

Desarrolló un método práctico y general para la hidrogenación regioselectiva de derivados de naftaleno funcionalizados.
La regioselectividad inusual se atribuye a una combinación de efectos electrónicos y estéricos en un proceso de adición de hidruro en tándem.
Esta metodología ofrece una herramienta valiosa para sintetizar compuestos y ligandos complejos a base de naftaleno.

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