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El cobre (II) anílidos en la aminación sp3 C-H

Eun Sil Jang¹, Claire L McMullin, Martina Käß

¹Department of Chemistry, Georgetown University , Box 571227-1227, Washington, D.C. 20057, United States.

Journal of the American Chemical Society

|June 19, 2014

Resumen

El nuevo cobre (II) anílidos facilitan las reacciones de aminación C-H. Estos complejos, cuando se combinan con un peróxido, permiten una nueva variante de la reacción de Kharasch-Sosnovsky para la síntesis funcional de anilina.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
La catálisis de la catálisis.
Síntesis orgánica La síntesis orgánica.

Sus antecedentes:

Los complejos de cobre son catalizadores versátiles en las transformaciones orgánicas.
Los ligandos β-diketiminato ofrecen propiedades estéricas y electrónicas sintonizables para complejos metálicos.
La aminación C-H es una reacción clave para introducir funcionalidades de nitrógeno en moléculas orgánicas.

Objetivo del estudio:

Para sintetizar y caracterizar el nuevo cobre β-diketiminato (II) anílidos.
Para investigar la actividad de aminación C-H de estos complejos de cobre.
Explorar un nuevo sistema catalítico para la síntesis de anilinas funcionalizadas.

Principales métodos:

Síntesis de cobre (II) anílidos a partir del cobre (II) t-butóxido y varias anilinas.
Caracterización estructural utilizando difracción de rayos X. Caracterización estructural utilizando difracción de rayos X. Caracterización estructural utilizando difracción de rayos X. Caracterización estructural utilizando difracción de rayos X. Caracterización estructural utilizando difracción de rayos X.
La susceptibilidad magnética y la espectroscopia de resonancia paramagnética de electrones (EPR).
Reacciones de aminación C-H con hidrocarburos en presencia y ausencia de tert-butilo hidroperoxido.

Principales resultados:

Se sintetizaron y caracterizaron nuevos anílidos de cobre (II) con diversos modos de enlace (κ(1) -N, puente, κ(2) -N,N).
La aminación estoiquiométrica C-H fue ineficaz con los anílidos de cobre solos.
Se logró una rápida aminación C-H utilizando peróxido de tert-butilo, lo que indica una vía radical que involucra a los radicales tert-butóxido.
Las anilidas de cobre actúan como carroñeros de radicales, lo que lleva a anilinas funcionalizadas a través de una reacción modificada de Kharasch-Sosnovsky.

Conclusiones:

Las anilidas sintetizadas β-diketiminato cobre (II) exhiben comportamientos de coordinación variados.
Estos complejos, junto con los peróxidos, permiten una variante amino eficiente de la reacción de Kharasch-Sosnovsky.
El estudio presenta un nuevo método para sintetizar anilinas funcionalizadas a través de la aminación C-H catalizada por cobre.

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