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Reorganización de los alcaloides biopaternada habilitada por la funcionalización de apertura de anillos de aminas

Hyeonggeun Lim¹, Sikwang Seong¹, Youyoung Kim^1,2

¹Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Korea.

Journal of the American Chemical Society

|November 16, 2021

Resumen

Este estudio introduce un nuevo método de funcionalización de apertura de anillos para aminas terciarias, que permite la conversión de productos naturales en valiosos metabolitos secundarios. La estrategia química versátil imita a la naturaleza

Área de la Ciencia:

Química orgánica
Síntesis de productos naturales
Biología Química

Sus antecedentes:

Las vías biosintéticas reorganizan con frecuencia los productos naturales, creando diversidad estructural.
Emulando las estrategias de reordenamiento de la naturaleza químicamente se pueden obtener metabolitos secundarios de valor agregado a partir de productos naturales abundantes.
El desarrollo de métodos químicos universales para la reorganización de moléculas complejas sigue siendo un desafío significativo.

Objetivo del estudio:

Desarrollar un método químico versátil y suave para la reorganización de productos naturales estructuralmente diversos.
Permitir la conversión de productos naturales fácilmente disponibles en otros metabolitos secundarios con valor añadido.
Explorar las reactividades químicas de los precursores biogenéticamente relevantes a través de reorganizaciones inspiradas.

Principales métodos:

Se informó de una nueva funcionalización de apertura de anillos de aminas terciarias.
Se utiliza el difluorocarbeno generado in situ para formar un producto intermedio de sales de amonio difluorometiladas.
Se emplean nucleófilos externos para atacar la posición α de la sal de amonio estabilizada.

Principales resultados:

Se ha demostrado la transformación exitosa de los alcaloides securinega, iboga y sarpagina en neosecurinega, chippiina/dippinina y alcaloides bisindol tipo vobasina, respectivamente.
Mostró la utilidad y la generalidad del método en la reorganización de alcaloides.
Exploró las reactividades químicas de los precursores biogenéticamente relevantes durante estas transformaciones.

Conclusiones:

El método de funcionalización de apertura de anillos desarrollado proporciona una herramienta poderosa para la diversificación estructural de los productos naturales.
Este enfoque ofrece una estrategia química para emular la diversificación basada en el reordenamiento de la naturaleza.
El método facilita la síntesis de alcaloides complejos y estructuras relacionadas.

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