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Migración de arilo de larga distancia catalizado por plata desde el centro de carbono al centro de nitrógeno

Taigang Zhou¹, Fei-Xian Luo¹, Ming-Yu Yang¹

¹Beijing National Laboratory of Molecular Sciences and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.

Journal of the American Chemical Society

|November 3, 2015

Resumen

Los investigadores informan de una nueva reacción catalizada por plata que rompe un enlace C-C y forma nuevos enlaces C-N a través de la migración de arilo. Este método produce eficazmente las valiosas γ-hidroxiaminas y los derivados de la tetrahidroquinolina.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

Los enlaces carbono-carbono (C-C) suelen ser inertes y difíciles de cortar selectivamente.
La migración de átomos a larga distancia en la síntesis orgánica es sintéticamente valiosa pero difícil de lograr.
El desarrollo de nuevos sistemas catalíticos para la formación de enlaces C-N es crucial para acceder a compuestos que contienen nitrógeno.

Objetivo del estudio:

Desarrollar una nueva estrategia sintética para la escisión selectiva de enlaces C-C.
Para lograr la migración de arilo de larga distancia de un carbono a un centro de nitrógeno utilizando la catálisis de plata.
Para sintetizar eficientemente las γ-hidroxiaminas y los derivados de la tetrahidroquinolina.

Principales métodos:

Utilizando la catálisis de plata (Ag) para mediar la reacción.
Investigando la escisión selectiva de un enlace C-C inerte.
Facilitando la migración de arilo desde un centro de carbono a uno de nitrógeno.
Caracterización de los productos de migración y su posterior conversión.

Principales resultados:

Se ha demostrado la escisión selectiva de un enlace C-C inerte.
Migración de arilo de larga distancia desde el carbono al nitrógeno.
Las γ-hidroximinas y los derivados de la tetrahidroquinolina sintetizados en rendimientos cuantitativos.
Los estudios mecanicistas preliminares sugirieron una vía radical.

Conclusiones:

Una nueva reacción catalizada por Ag permite la escisión selectiva de enlaces C-C y la formación de enlaces C-N a través de la migración de arilo.
El método desarrollado proporciona un acceso eficiente a importantes bases de γ-hidroxiamina y tetrahidroquinolina.
La reacción probablemente procede a través de un mecanismo radical, ofreciendo ideas para el desarrollo sintético futuro.

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