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Reacciones organocatalíticas asimétricas tio-Diels-Alder a través de la catálisis de la trienamina

Hao Jiang¹, David Cruz Cruz, Yang Li

¹Center for Catalysis, Department of Chemistry, Aarhus University , Langelandsgade 140, DK-8000 Aarhus C, Denmark.

Journal of the American Chemical Society

|March 12, 2013

Resumen

Este estudio introduce una innovadora reacción catalítica asimétrica tio-Diels-Alder para la creación de heterociclos de azufre enriquecidos con enantio. El nuevo método supera los desafíos con los tiocarboniles, produciendo compuestos valiosos con alta selectividad.

Área de la Ciencia:

Química orgánica es la química orgánica.
Catalización asimétrica por catálisis asimétrica.
Química Heterocíclica La Química Heterocíclica es una de las más conocidas.

Sus antecedentes:

Los tiocarboniles son difíciles dienófilos en las reacciones enantioselectivas de Diels-Alder debido a la reactividad y la mala coordinación del catalizador.
El desarrollo de métodos eficientes para los heterociclos basados en azufre es crucial en la química sintética.

Objetivo del estudio:

Para reportar una nueva reacción catalítica asimétrica de tio-Diels-Alder.
Para superar los desafíos asociados con el uso de tiocarboniles en reacciones enantioselectivas.
Para sintetizar heterociclos basados en azufre altamente enriquecidos con enantio.

Principales métodos:

Utilizó una reacción catalítica asimétrica de tio-Diels-Alder.
Empleó una estrategia que involucraba dienes enlazados a catalizadores generados in situ.
Realizó cálculos de la Teoría Funcional de Densidad (DFT) para dilucidar el mecanismo de reacción.

Principales resultados:

Se han logrado altos rendimientos y selectividades de altas a excelentes para los heterociclos basados en azufre.
Síntesis de dihidrothiopiranos sintéticamente útiles y otros heterociclos complejos que contienen azufre.
Demostró la aplicación exitosa de la reacción desarrollada para acceder a compuestos ópticamente activos.

Conclusiones:

La reacción de tio-Diels-Alder desarrollada proporciona una nueva y efectiva ruta a los heterociclos de azufre enriquecidos con enantio.
La estrategia de usar dienos enlazados a catalizadores generados in situ aborda con éxito las limitaciones de la reactividad del tiocarbonyl.
Los productos ópticamente activos pueden someterse a más transformaciones sintéticas, ampliando su utilidad.

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