Monodefluoroborilación regioselectiva catalizada por el cobre de los polifluoroalquenos en ruta hacia diversos fluoroalquenos
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Published on: July 28, 2018
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Hironobu Sakaguchi1, Yuta Uetake2, Masato Ohashi1
1Department of Applied Chemistry, Faculty of Engineering, Osaka University , 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan.
Journal of the American Chemical Society
|August 30, 2017
Resumen
La monodefluoroborilación catalizada por el cobre de los polifluoroalquenos ofrece un método versátil para sintetizar valiosos derivados de los fluoroalquenos. Esta reacción procede con un amplio alcance de sustrato y una mayor practicidad sintética, lo que permite la creación de moléculas complejas como los imitadores de fármacos.
Área de la Ciencia:
- Química orgánica
- Catálisis
- Química del fluor
Sus antecedentes:
- Los polifluoroalquenos son componentes importantes en la síntesis orgánica.
- El desarrollo de métodos eficientes para su funcionalidad es crucial.
- La monodefluoroborilación ofrece una vía para introducir selectivamente grupos funcionales de boro.
Objetivo del estudio:
- Desarrollar una monodefluoroborilación regioselectiva catalizada por el cobre de los polifluoroalquenos.
- Explorar el alcance y las limitaciones de este nuevo método sintético.
- Demostrar la utilidad de los compuestos de fluoroalquenilborón resultantes en otras transformaciones.
Principales métodos:
- Reacción catalizada por el cobre de varios polifluoroalquenos con reactivos de diboro.
- Optimización de las condiciones de reacción, incluidos el catalizador, el solvente y la temperatura.
- Investigación de diferentes fuentes de boro, como el bis (pinacolato) diboro y el bis (neopentyl glycolato) diboro.
- Derivación de productos a sales de trifluoroborato de potasio para una mayor estabilidad y aislamiento.
Principales resultados:
- Se ha logrado la borilación monodefluoro selectiva de una amplia gama de polifluoroalquenos, incluidos los (difluorovinil) arenos, el tetrafluoroetileno, los (trifluorovinil) arenos y los monofluoroalquenos trifluorometilados.
- Fuentes óptimas de boro identificadas ((Bpin) 2 y (Bnep) 2) en función de las propiedades electrónicas del grupo arilo en las arenas (difluorovinilo).
- Se ha demostrado una mayor viabilidad sintética mediante el aislamiento de sales estables de trifluoroborato de potasio.
- Se ha demostrado que la regioselectividad se rige por el modo de eliminación de la β-fluorina, que es dependiente del sustrato.
Conclusiones:
- La monodefluoroborilación catalizada por cobre desarrollada es un método suave, regioselectivo y de amplia aplicación.
- El aislamiento fácil de las sales de trifluoroborato aumenta la utilidad sintética de la reacción.
- Los compuestos de fluoroalquenilborón sintetizados se pueden transformar fácilmente en derivados valiosos, incluidos los posibles agentes farmacéuticos.
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