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Síntesis, caracterización y actividades catalíticas únicas de un enolato de níquel fluorado

Ryohei Doi¹, Kotaro Kikushima, Masato Ohashi

¹Department of Applied Chemistry, Faculty of Engineering, Osaka University , Suita, Osaka 565-0871, Japan.

Journal of the American Chemical Society

|February 20, 2015

Resumen

Los investigadores sintetizaron un nuevo complejo de enolato de níquel con átomos de flúor. Este nuevo complejo demuestra aplicaciones catalíticas únicas en reacciones de Tishchenko y esterificación cruzada selectiva de trifluoroacetofenonas.

Área de la Ciencia:

Química organometálica Química orgánica de los metales.
Química del flúor Química del flúor
La catálisis de la catálisis.

Sus antecedentes:

Los complejos de enolado de níquel son valiosos intermediarios sintéticos.
La activación del enlace C-F es una transformación desafiante pero importante en la síntesis orgánica.
Los compuestos orgánicos fluorados tienen propiedades y aplicaciones únicas.

Objetivo del estudio:

Para sintetizar y caracterizar un nuevo complejo de enolato de níquel con átomos de flúor.
Para investigar la química de coordinación y la reactividad del nuevo complejo.
Para explorar sus aplicaciones catalíticas en transformaciones orgánicas.

Principales métodos:

Síntesis del complejo de enolato de níquel a través de la activación del enlace C-F promovido por B ((C6F5) 3).
Difracción de rayos X para elucidación estructural.
Reacciones con isocyanuros y aldehídos.
Espectroscopia de RMN para la caracterización.
Estudios catalíticos para reacciones de Tishchenko y esterificación cruzada.

Principales resultados:

Síntesis exitosa de un nuevo complejo de enolato de níquel fluorado, [PhCOCF2) Ni (dcpe) ][FB (C6F5) ].
La difracción de rayos X confirmó un modo de coordinación η(3)-oxalilo.
El complejo reacciona con los isocyanuros para formar enolados unidos a C y con aldehídos para producir productos de inserción.
Actividad catalítica demostrada en reacciones de esterificación cruzada de Tishchenko y selectiva.

Conclusiones:

El nuevo complejo de enolado de níquel es un reactivo versátil para la activación de enlaces C-F y las transformaciones posteriores.
El complejo exhibe propiedades catalíticas únicas para Tishchenko y reacciones de esterificación cruzada que involucran cetonas fluoradas.
Este trabajo amplía el alcance de la química del organonickel y la síntesis de compuestos fluorados.

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