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Síntesis total convergente de la papililona A a través de la cascada de alquenilación/ciclización Pd catalizada

Xing-Qian Shan¹, Xiang Zhang¹, Peng-Fei Lian¹

¹School of Pharmaceutical Sciences, Shanghai Key Laboratory of Chiral Drugs and Engineering, Shanghai Frontiers Science Center of Drug Target Identification and Delivery, National Key Laboratory of Innovative Immunotherapy, Shanghai Jiao Tong University, Shanghai 200240, China.

Journal of the American Chemical Society

|November 28, 2025

Resumen

Los investigadores lograron la primera síntesis total del compuesto antiinflamatorio papililona A. Esta síntesis de nueve pasos construyó eficientemente su estructura compleja, incluidos los centros cuaternarios desafiantes, utilizando una nueva estrategia de cascada de ciclización.

Área de la Ciencia:

Química orgánica
Química sintética
Síntesis de productos naturales

Sus antecedentes:

Papililone A es un diterpenoide policíclico único con propiedades antiinflamatorias.
Su complejo esqueleto tetraciclico y múltiples estereocentros presentan desafíos sintéticos significativos.

Objetivo del estudio:

Para lograr la primera síntesis total de papililona A.
Desarrollar una vía sintética eficiente y concisa para este complejo producto natural.

Principales métodos:

Se empleó una síntesis total de la secuencia lineal más larga (LLS) de nueve pasos.
Las estrategias clave incluyeron una cascada de ciclización, alquenilación catalizada por Pd / ciclización endo-trig, cascada de ciclización polar-radical, acoplamiento de fragmentos y reordenamiento de α-cetol vinílogo.
La síntesis se realizó sin el uso de grupos protectores.

Principales resultados:

La síntesis construyó con éxito el marco tricíclico 5/5/6 con puente fundido y dos estereocentros contiguos en un solo paso.
El sistema de anillos 5/5 bicíclicos fundidos y los estereocentros cuaternarios de carbono vecinos se forjaron estereoselectivamente.
La síntesis confirmó la configuración β-metilo en C17 como la estereoquímica auténtica de la papililona A.

Conclusiones:

Se logró la primera síntesis total de papililona A.
La estrategia sintética desarrollada es concisa y eficiente, superando obstáculos sintéticos significativos.
Este trabajo resuelve ambigüedades estereoquímicas y facilita una mayor investigación biológica de la papililona A.

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