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Enfoque sintético divergente para los diterpenoides de grayanano

An Zhu¹, Yumeng Lyu², Qidong Xia³

¹Department of Chemistry, Zhejiang University, Hangzhou 310058, China.

Journal of the American Chemical Society

|April 7, 2023

Resumen

Los investigadores sintetizaron nueve diterpenoides de grayanano, incluidos seis compuestos nuevos, utilizando una estrategia divergente. Las transformaciones clave permitieron la construcción de diversos esqueletos de grayanane y ofrecieron información sobre sus relaciones biosintéticas.

Área de la Ciencia:

Química orgánica
Síntesis de productos naturales
Química medicinal

Sus antecedentes:

Los diterpenoides de grayanano son una clase de productos naturales con estructuras complejas.
Estos compuestos exhiben una amplia gama de actividades biológicas.
Los esfuerzos sintéticos anteriores han sido limitados en alcance y eficiencia.

Objetivo del estudio:

Desarrollar una estrategia sintética divergente para acceder a diversos diterpenoides de grayanos.
Para lograr la síntesis total de nueve diterpenoides de grayanano, incluidos seis compuestos nuevos.
Para aclarar las relaciones biosintéticas entre los diferentes esqueletos grayanane.

Principales métodos:

Cascada de reordenamiento de cicloadición/pinacol inducida por desaromatización oxidativa [5 + 2] para el ensamblaje de anillos de CD.
Reorganización de la fotosantonina para la construcción de las bicicletas 5/7 (anillos AB) de 1-epi-grayanoides.
Proceso de fragmentación de grube/carbonileno para el acceso a esqueletos grisáceos adicionales.

Principales resultados:

Se ha obtenido la síntesis total de nueve diterpenoides grayananos (GTX-II, GTX-III, rodijaponina III, GTX-XV, principinol D, iso-GTX-II, 1,5-seco-GTX-Δ1,10-eno, leucótoles B y D).
Seis de los compuestos sintetizados representan las primeras síntesis totales reportadas.
El enfoque divergente generó con éxito cinco subtipos distintos de grayanana.
Los cálculos de la teoría funcional de la densidad proporcionaron información mecanicista sobre las transformaciones clave.

Conclusiones:

Se estableció una estrategia sintética concisa y divergente para los diterpenoides de grayanano.
La metodología permite la construcción eficiente de complejos esqueletos de grayanane.
El estudio proporciona información valiosa sobre la biosíntesis de estos productos naturales.

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