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Síntesis enantioselectiva de heterociclos de anillo medio, éteres terciarios y alcoholes terciarios por metátesis de

Andrew F Kiely¹, Jesper A Jernelius, Richard R Schrock

¹Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, USA.

Journal of the American Chemical Society

|March 21, 2002

Resumen

La metátesis asimétrica de cierre de anillos catalizada por molibdeno produce eficientemente heterociclos insaturados de anillo medio con alta enantioselectividad. Estos compuestos sirven como precursores de valiosos alcoholes terciarios.

Área de la Ciencia:

Química orgánica es la química orgánica.
La catálisis es la catálisis.
Química sintética de la química sintética.

Sus antecedentes:

La síntesis asimétrica es crucial para producir compuestos enantioméricamente puros.
La metatesis de cierre de anillo es una herramienta poderosa para la formación de estructuras cíclicas.
El acceso a los heterociclos de anillo medio enantioselectivamente sigue siendo un desafío sintético.

Objetivo del estudio:

Desarrollar un método altamente enantioselectivo para la síntesis de heterociclos insaturados de anillo medio.
Explorar la utilidad de la metátesis asimétrica de cierre de anillo catalizada por molibdeno (ARCM).
Para demostrar la versatilidad sintética de los productos obtenidos.

Principales métodos:

Metátesis asimétrica de cierre de anillo catalizada por molibdeno (ARCM) de los trienos achirales.
Optimización de la reacción en la escala de Gram.
Condiciones de reacción sin disolventes.

Principales resultados:

Altos rendimientos y excelente enantioselectividad en la formación de heterociclos insaturados de anillo medio.
La expansión exitosa de la reacción ARCM a cantidades de gramos.
Se ha demostrado la funcionalización de los siloxanos enantioselectivos en alcoholes terciarios.

Conclusiones:

El ARCM catalizado por molibdeno es una estrategia efectiva para acceder a los heterociclos de anillo medio enriquecidos enantioméricamente.
El método desarrollado ofrece una ruta práctica y escalable a valiosos intermedios sintéticos.
Los siloxanos insaturados resultantes proporcionan acceso a alcoholes terciarios difíciles de sintetizar.

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