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La monoarilación selectiva suave catalizada por el paladio de los nitriles

Lingyun Wu¹, John F Hartwig

¹Department of Chemistry, Yale University, New Haven, Connecticut 06510, USA.

Journal of the American Chemical Society

|November 10, 2005

Resumen

Nuevos métodos catalizados por paladio permiten una arilación eficiente de los nitriles en condiciones más suaves. Estas reacciones crean nitriles bencílicos valiosos, importantes en productos farmacéuticos y en la síntesis, utilizando nitriles alfa-sililo o reactivos de zinc.

Área de la Ciencia:

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

Sus antecedentes:

Las reacciones de acoplamiento cruzado catalizadas por paladio son cruciales en la síntesis orgánica.
Los métodos tradicionales de arilación de nitrilo a menudo requieren condiciones básicas duras, lo que limita la compatibilidad del grupo funcional.

Objetivo del estudio:

Desarrollar nuevos procedimientos catalizados por paladio para la arilación de nitrilo bajo condiciones más suaves y menos básicas.
Ampliar la utilidad sintética de los nitriles bencílicos a través de rutas catalíticas eficientes.

Principales métodos:

Desarrolló dos estrategias de arilación catalizadas por el paladio para los nitriles.
Se utilizan nitriles alfa-sililo con ZnF2 para la monoarilación selectiva de nitriles primarios.
Se emplean reactivos de cianoalquilo de zinc para la arilación de nitriles secundarios.

Principales resultados:

Se ha logrado la monoariación selectiva de acetonitrilo y nitrilos primarios con una amplia tolerancia de grupo funcional.
Se obtienen altos rendimientos en la arilación de nitriles secundarios en condiciones de tolerancia a las bases.
Demostró la síntesis de verapamil, un medicamento cardiovascular, mostrando la aplicación práctica de estos métodos.

Conclusiones:

Los métodos desarrollados ofrecen rutas catalíticas eficientes y versátiles a diversos nitriles bencílicos.
Estos procedimientos son compatibles con varios grupos funcionales sensibles a bases, mejorando el alcance sintético.
Las nuevas reacciones de acoplamiento proporcionan una herramienta valiosa para acceder a compuestos biológicamente significativos e intermedios sintéticos.

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