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Síntesis asimétrica catalizada por el paladio de fluoruros alilicos catalizados por el paladio

Matthew H Katcher¹, Abigail G Doyle

¹Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.

Journal of the American Chemical Society

|November 20, 2010

Resumen

Los investigadores desarrollaron un método sencillo para la fluoración enantioselectiva de cloruros alílicos cíclicos utilizando un catalizador de paladio. Esto proporciona acceso a valiosos fluoruros alelicos cíclicos enriquecidos con enantio con diversos grupos funcionales.

Área de la Ciencia:

Química orgánica es la química orgánica.
Química organometálica Química orgánica de los metales.
Fluoración Química de la fluoración

Sus antecedentes:

Las reacciones catalizadas por el paladio son cruciales en la síntesis orgánica.
La fluoración nucleofílica presenta desafíos para lograr una alta enantioselectividad.
Los cloruros alílicos cíclicos son precursores sintéticos versátiles.

Objetivo del estudio:

Desarrollar un método de fluoración enantioselectiva eficiente para los cloruros alílicos cíclicos.
Explorar el uso del fluoruro de plata (AgF) como fuente de fluoruro en la catálisis del paladio.
Para sintetizar fluoruros alelicos cíclicos altamente enriquecidos con enantio.

Principales métodos:

Utilizó un catalizador Pd(0) en combinación con un ligando de bisfosfina de Trost.
Empleó cloruros cíclicos alilicos fácilmente disponibles como sustratos.
Investigó el mecanismo de reacción, incluida la evidencia de un ataque de tipo S(N) 2.

Principales resultados:

Se logró una fluoración enantioselectiva exitosa de cloruros alílicos cíclicos utilizando AgF.
Se ha demostrado una facilidad de operación sin precedentes para la fluoración nucleofílica mediada por paladio.
Fluoruros alelicos cíclicos sintetizados con alto enriquecimiento enantiomérico y diversos grupos funcionales.

Conclusiones:

El método desarrollado ofrece una ruta fácil a valiosos compuestos fluorados quirales.
La reacción procede a través del ataque nucleófilo del fluoruro sobre un intermediario Pd (II) -alilo.
Este trabajo amplía el alcance de las estrategias de fluoración enantioselectiva en la síntesis orgánica.

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