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La aminofluorización intramolecular catalizada por el paladio de alquenos no activados

Tao Wu¹, Guoyin Yin, Guosheng Liu

¹State Key Laboratory of Organometallics Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Science, 354 Fenglin Road, Shanghai, China, 200032.

Journal of the American Chemical Society

|October 28, 2009

Resumen

Los investigadores desarrollaron una nueva reacción catalizada por el paladio para crear fluoroaminas vecinas a partir de alquenos no activados. Este método utiliza fluoruro de plata (AgF) y un reactivo de yodo hipervalente, logrando una alta regioselectividad en la formación de enlaces C-F.

Área de la Ciencia:

Química orgánica es la química orgánica.
La catálisis de la catálisis.
Fluoración Química de la fluoración

Sus antecedentes:

Las reacciones catalizadas por el paladio son cruciales en la síntesis orgánica moderna.
El desarrollo de métodos eficientes para la formación de bonos C-F sigue siendo un desafío significativo.
Las reacciones intramoleculares ofrecen ventajas en el control de la selectividad.

Objetivo del estudio:

Desarrollar una nueva aminofluoración oxidativa intramolecular catalizada por el paladio de alquenos no activados.
Para utilizar reactivos fácilmente disponibles como el fluoruro de plata (AgF) y los compuestos de yodo hipervalentes.
Para lograr una alta regioselectividad en la síntesis de productos fluoroamínicos vecinos.

Principales métodos:

El empleo de un catalizador de paladio para la aminofluoración oxidativa intramolecular.
Utilizando el fluoruro de plata (AgF) como fuente de fluoración.
Utilizando PhI(OPiv) 2 como el oxidante en el sistema de reacción.

Principales resultados:

Síntesis exitosa de productos fluoroamínicos vecinos de alquenos no activados.
Demostración de una regioselectividad muy alta en el proceso de aminofluoración.
Propuso un ciclo catalítico que involucra al paladio en los estados de oxidación Pd (II) y Pd (IV).

Conclusiones:

El método desarrollado proporciona una ruta eficiente a las fluoroaminas vecinas.
Los estudios mecanicistas preliminares sugieren un ciclo catalítico Pd (II/IV) con eliminación reductiva favorecida.
La reacción ofrece una herramienta valiosa para introducir funcionalidades de flúor y amina simultáneamente.

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