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Cicloadiciones de Furan Diels-Alder promovidas por hidrosilación con estereoselectividad controlada por el grupo

Zhi-Yun Liu¹, Ming Zhang¹, Xiao-Chen Wang¹

¹State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry , Nankai University , Tianjin 300071 , China.

Journal of the American Chemical Society

|December 7, 2019

Resumen

Una nueva reacción catalizada por B ((C6F5) 3) permite la síntesis en cascada de moléculas complejas a partir de N-alil-N-furiliamidas. El volumen estérico de grupos silílicos controla la estereoquímica del producto en esta nueva secuencia de escisión de Diels-Alder y éter.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

Las reacciones de Furan Diels-Alder son valiosas para sintetizar moléculas orgánicas complejas.
Las reacciones convencionales de furano Diels-Alder a menudo tienen limitaciones en el alcance del sustrato y el control estereoquímico.

Objetivo del estudio:

Desarrollar una nueva reacción en cascada para las N-alil-N-furiliamidas.
Para explorar la actividad catalítica de B ((C6F5) 3) en una cascada de furano Diels-Alder.
Investigar la influencia de los grupos silílicos en la vía de reacción y la estereoquímica.

Principales métodos:

B(C6F5) 3-reacción en cascada catalizada de las N-alil-N-furiliamidas.
Reacción intramolecular de furano Diels-Alder seguida por la escisión del éter.
Grupos silílicos variados (Et3SiH, iPr3SiH) para el estudio de los resultados estereoquímicos.
Experimentos de control y estudios computacionales para elucidar el mecanismo.

Principales resultados:

Se logró una reacción en cascada sin precedentes que involucra la escisión de furano Diels-Alder y éter.
La reacción demostró un amplio alcance de sustrato, acomodando las olefinas estéricamente obstaculizadas.
La diastereoselectividad fue controlada por la masa estérica del grupo sililo, con diferentes grupos sililo que producen diastereómeros distintos.
Los estudios computacionales confirmaron el papel de los estéricos del grupo sililo en la dirección de la vía de reacción.

Conclusiones:

La reacción en cascada catalizada B ((C6F5) 3) desarrollada ofrece una nueva y poderosa herramienta para la síntesis orgánica.
Esta metodología supera las limitaciones de las reacciones tradicionales de Diels-Alder con respecto al alcance del sustrato y el estereocontrol.
La influencia estérica de los grupos silílicos proporciona un mecanismo para controlar la diastereoquímica del producto.

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