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Síntesis total enantioselectiva de (+) -psiguadial B

Lauren M Chapman¹, Jordan C Beck¹, Linglin Wu¹

¹The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.

Journal of the American Chemical Society

|July 26, 2016

Resumen

Este estudio informa de la primera síntesis total enantioselectiva de (+) -psiguadial B, un producto natural citotóxico. Los pasos clave involucraron la adición asimétrica de ceteno, la alquenilación C ((sp3) -H y la metátesis de cierre de anillo para la construcción de la estructura de terpenos.

Área de la Ciencia:

Química orgánica
Síntesis de productos naturales
Catálisis asimétrica

Sus antecedentes:

(+) - Psiguadial B es un producto natural citotóxico con una estructura compleja de terpenos biciclo [4.3.1].
La síntesis enantioselectiva de productos naturales complejos sigue siendo un desafío importante en la química orgánica.

Objetivo del estudio:

Para lograr la primera síntesis total enantioselectiva de (+) -psiguadial B.
Desarrollar nuevas estrategias sintéticas para construir el intrincado núcleo de terpenos.

Principales métodos:

Preparación enantioselectiva de un intermediario clave de ciclobutan a través del reordenamiento en tándem de Wolff y la adición asimétrica de ceteno.
Alquenilación dirigida C ((sp3) -H para la formación de enlaces estratégicos C1-C2.
Metátesis de cierre de anillo para ensamblar el marco de biciclo[4.3.1]decano.

Principales resultados:

Síntesis total enantioselectiva exitosa de (+) psiguadial B.
Demostración de una nueva combinación de reordenamiento de Wolff y adición asimétrica de ceteno para la formación de ciclobutano.
Se emplean estrategias eficientes de funcionalización de C ((sp3) -H y de metátesis de cierre de anillo.

Conclusiones:

La vía sintética desarrollada proporciona acceso al (+) -psiguadial B con alta enantioselectividad.
La metodología destaca la utilidad de la adición asimétrica de ceteno y la alquenilación C ((sp3) -H en la síntesis de moléculas complejas.
Este trabajo establece un precedente para la síntesis de productos naturales relacionados con los terpenos.

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