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Síntesis total de (-) -Spinosyn A a través de la macrolactonización carbonilada

Yu Bai¹, Xingyu Shen¹, Yong Li¹

¹Department of Chemistry and Center for Cancer Research, Purdue University , West Lafayette, Indiana 47907, United States.

Journal of the American Chemical Society

|August 12, 2016

Resumen

Los investigadores lograron una síntesis total eficiente de (-) -spinosyn A, un componente clave del insecticida orgánico spinosad. Este avance permite la creación de análogos de spinosyn para combatir la resistencia a los insecticidas.

Área de la Ciencia:

Química orgánica
Síntesis de productos naturales
Química medicinal

Sus antecedentes:

Spinosyn A es el componente principal de spinosad, un insecticida orgánico ampliamente utilizado aprobado por la FDA.
La compleja estructura tetraciclica del Spinosad presenta desafíos sintéticos significativos.
Los problemas emergentes de resistencia cruzada requieren el desarrollo de nuevos análogos de spinosyn.

Objetivo del estudio:

Desarrollar una síntesis total eficiente y convergente de (-) -spinosina A.
Establecer una vía sintética modular para la generación de análogos de spinosyn.
Proporcionar una plataforma para abordar la resistencia a los insecticidas.

Principales métodos:

Una síntesis de 15 pasos con una reacción intramolecular de Diels-Alder catalizada por aminas quirales.
Reorganización de acetato propargílico catalizado por oro y glicosilación Yu para instalaciones estructurales clave.
La macrolactonización carbonilativa Heck catalizada por el paladio para la formación de macrolactonas.

Principales resultados:

Se ha logrado la síntesis total de (-) -spinosina A en un total de 23 pasos.
Se logra una alta diastereoselectividad en la reacción de Diels-Alder.
Formación eficiente de la macrolactona fusionada 5,12 y instalación de la β-forosamina.

Conclusiones:

La estrategia sintética desarrollada es altamente convergente y modular.
Este enfoque facilita la síntesis de diversos análogos de la espinosina.
La metodología ofrece una vía para superar los problemas de resistencia cruzada a los insecticidas.

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