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Hidroaminación de alquenos no activados con azidas alifáticas

Si-Ming Jia¹, Yi-Hang Huang¹, Zhan-Lin Wang¹

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

Journal of the American Chemical Society

|September 1, 2022

Resumen

Este estudio presenta un método eficiente para la hidroaminación anti-Markovnikov de alquenos utilizando azidas alifáticas y silano. La reacción en cadena radical logra una alta diastereoselectividad, ofreciendo una nueva ruta sintética.

Área de la Ciencia:

Química orgánica
Metodología sintética

Sus antecedentes:

Las reacciones de hidroaminación son cruciales para sintetizar compuestos que contienen nitrógeno.
El desarrollo de métodos selectivos para alquenos no activados sigue siendo un desafío.

Objetivo del estudio:

Informar sobre una hidroaminación anti-Markovnikov intermolecular eficiente y altamente diastereoselectiva de alquenos no activados.
Explorar el mecanismo de reacción e identificar los factores clave para la selectividad.

Principales métodos:

Utilizando una vía de cadena radical mediada por silano.
Utilizan una amplia gama de azidas alifáticos y alquenos no activados.
Realización de estudios mecanicistas y computacionales.

Principales resultados:

Se ha logrado una hidroaminación anti-Markovnikov intermolecular eficiente y altamente diastereoselectiva.
Tolerancia demostrada a diversos azidos y alquenos, con el alqueno como reactivo limitante.
Identificó un mecanismo de cadena radical que involucra la formación de radicales de aminio, la adición de alquenos y la transferencia de átomos de hidrógeno (HAT) desde el silano.

Conclusiones:

El método desarrollado proporciona una herramienta valiosa para sintetizar moléculas complejas.
Los silanos estérilmente voluminosos son clave para lograr una alta diastereoselectividad en el paso HAT.
El análisis computacional aclaró el mecanismo de activación de azida y formación de radicales aminílicos.

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