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Acoplamiento cruzado catalizado por cobre de pronucleófilos de silicio con electrófilos de alquilo no activados
Weichao Xue1, Zheng-Wang Qu2, Stefan Grimme2
1Institut für Chemie, Technische Universität Berlin , Strasse des 17. Juni 115, 10623 Berlin, Germany.
Journal of the American Chemical Society
|October 18, 2016
Resumen
Este estudio introduce una nueva reacción catalizada por el cobre que forma enlaces carbono-silicio a partir de compuestos alifáticos. El proceso utiliza radicales alquilo para la ciclización eficiente y la formación de enlaces, ofreciendo una nueva vía sintética.
Área de la Ciencia:
- Química orgánica
- Química del silicio orgánico
- Catálisis
Sus antecedentes:
- La formación de enlaces carbono-silicio es crucial en la síntesis orgánica.
- El desarrollo de métodos eficientes para el acoplamiento cruzado C ((sp3) -Si sigue siendo un reto.
- Las reacciones mediadas por radicales ofrecen vías alternativas para la construcción de enlaces.
Objetivo del estudio:
- Informar de una nueva reacción de acoplamiento cruzado C(sp3)-Si catalizada por el cobre.
- Para utilizar electrófilos alifáticos C ((sp3) -I y un reactivo Si-B.
- Elucidar el mecanismo que involucra a los radicales alquilo intermedios y la ciclización.
Principales métodos:
- Reacción de acoplamiento cruzado catalizada por cobre.
- Utilización de reactivos de silicio y boro como pronucleófilos de silicio.
- Cálculos químicos cuánticos para el análisis mecanicista.
Principales resultados:
- Se ha realizado con éxito el acoplamiento cruzado C(sp3)-Si de yoduros alifáticos.
- Observación de los radicales alquilo intermedios que participan en las ciclizaciones 5-exo-trig.
- Altos rendimientos y excelente control diastereo para los precursores del tipo Ueno-Stork.
Conclusiones:
- Se ha establecido una nueva ruta sintética para la formación de enlaces C ((sp3) -Si.
- La reacción procede a través de una vía radical catalizada por cobre con ciclización intramolecular.
- Las ideas mecanicistas se obtuvieron a través del análisis computacional, detallando la liberación de nucleófilos y los procesos radicales.
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