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Síntesis estereoselectiva de un enlace de Salomón topológicamente quiral

Zheng Cui¹, Ye Lu¹, Xiang Gao¹

¹State Key Laboratory of Molecular Engineering of Polymers, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, People's Republic of China.

Journal of the American Chemical Society

|August 14, 2020

Resumen

Los investigadores lograron una síntesis estereoselectiva de un enlace quiral de Solomon utilizando autoensamblaje impulsado por coordinación y ligandos quirales. Este método permite la creación de enantiómeros topológicos específicos a través de procesos de autoensamblaje controlados.

Área de la Ciencia:

Química supramolecular
Síntesis orgánica
Química de coordinación

Sus antecedentes:

Los isómeros topológicos, como los enlaces de Salomón, presentan desafíos estructurales únicos en la síntesis.
La síntesis estereoselectiva es crucial para acceder a enantiómeros específicos de arquitecturas moleculares complejas.
Los ligandos quirales axialmente ofrecen una herramienta poderosa para inducir la quiralidad en estructuras autoensambladas.

Objetivo del estudio:

Para lograr la síntesis estereoselectiva de un enlace de Salomón topológicamente quiral.
Explorar el uso del autoensamblaje impulsado por la coordinación para construir estructuras topológicas complejas.
Investigar el papel de los ligandos quirales axialmente en el control de la enantioselectividad durante el autoensamblaje.

Principales métodos:

Para diseñar la estrategia sintética se empleó el análisis retrosintético.
Se realizó un autoensamblaje impulsado por la coordinación utilizando complejos de iridio binucleares y ligandos quirales axialmente ((R o S) -2,2'-dietoxi-1,1'-binaftil-6,6'-bis-vinilpiridina)).
El proceso de autoensamblaje involucró el complejo de iridio binuclear [Cp*2Ir2 ((DHBQ) ((OTf)) ] (Ir-B ((OTf)) ].

Principales resultados:

Se realizó con éxito la síntesis diastereoselectiva de enantiómeros topológicos (P y M) de un enlace de Salomón.
La combinación de ligandos quirales específicos (R-L o S-L) con el complejo de iridio dictó la formación del enantiómero P o M, respectivamente.
Las interacciones π-π entre los ligandos quirales se identificaron como la principal fuerza impulsora para la formación de enlaces de Solomon.

Conclusiones:

Se ha logrado una síntesis estereoselectiva muy esperada de un enlace de Solomon topológicamente quiral.
El autoensamblaje impulsado por la coordinación junto con la inducción quiral por ligandos quirales axialmente es una estrategia efectiva para crear estructuras topológicas complejas.
El estudio demuestra un control preciso sobre la formación de enantiómeros de enlace de Salomón a través de la selección de ligandos.

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