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Diorganocupratos mixtos monoméricos y diméricos aislados basados en los voluminosos ligandos de "corteza" de tamaño
Mikinao Ito1, Daisuke Hashizume, Takeo Fukunaga
1Functional Elemento-Organic Chemistry Unit, RIKEN Advanced Science Institute, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Journal of the American Chemical Society
|December 1, 2009
Resumen
Los investigadores sintetizaron nuevos complejos mixtos de diorganocópero (I) utilizando ligandos Rind. El complejo monomérico resultante acopla selectivamente dos grupos orgánicos diferentes, lo que hace avanzar la química organometálica.
Área de la Ciencia:
- Química organometálica Química orgánica de los metales.
- Química sintética de la química sintética.
- La catálisis de la catálisis.
Sus antecedentes:
- Los complejos de diorganocobre (I) son reactivos cruciales en la síntesis orgánica.
- El aislamiento y la caracterización de los complejos mixtos de diorganocobre (I) presentan desafíos sintéticos debido a su reactividad e inestabilidad.
Objetivo del estudio:
- Para sintetizar y caracterizar estructuralmente nuevos y aislables complejos mixtos de diorganocobre.
- Para investigar la reactividad de estos complejos en reacciones de acoplamiento cruzado.
Principales métodos:
- Síntesis de ligandos Rind voluminosos basados en un esqueleto de s-hidrindaceno sustituido por octa-R con anillo fundido.
- Reacción de RindLi con bromuro de cobre (CuBr) para formar dimeros o monómeros de organobromocuprato.
- Sustitución de bromo con litio trimetilsililacetilida para obtener complejos mixtos de arilo ((alquinilo) cobre ((I)).
Principales resultados:
- Se han sintetizado con éxito y caracterizado estructuralmente complejos diméricos y monoméricos de arilo (alquinilo) cobre (I) complejos.
- El Complejo B, un diorganocuprato monomérico mixto (LiCuRR'), es el primer ejemplo aislable de su tipo.
- El complejo B demostró el acoplamiento cruzado oxidativo selectivo de dos grupos orgánicos distintos unidos al cobre.
Conclusiones:
- La masa estérica de los ligandos de Rind dicta la formación de cupratos monoméricos o diméricos.
- El desarrollo de monómeros diorganocupratos mixtos aislables expande el alcance de las transformaciones orgánicas mediadas por el cobre.
- Estos nuevos complejos ofrecen una plataforma para reacciones selectivas de acoplamiento cruzado, mejorando la utilidad sintética.
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