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La difuncionalización catalizada por el paladio de éteres enoles a aminoácetales con aminos y alcoholes

Yinjun Xie¹, Jianhua Hu, Pan Xie

¹State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences , Lanzhou 730000, People's Republic of China.

Journal of the American Chemical Society

|November 22, 2013

Resumen

Una nueva difuncionalización catalizada por el paladio de éteres enol utilizando aminos y alcoholes crea aminoácetales. Esta estrategia intercepta los principales intermediarios entre el paladio y el alquilo, lo que permite una nueva vía sintética.

Área de la Ciencia:

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

Sus antecedentes:

La reacción de Heck es una piedra angular del acoplamiento cruzado catalizado por paladio.
Las especies de alquilo de paladio son intermediarios clave en muchas reacciones catalizadas por el paladio.
El control de la reactividad de los intermediarios de paladio-alquilo es crucial para el desarrollo de nuevas transformaciones.

Objetivo del estudio:

Para desarrollar una nueva reacción de difuncionalización catalizada por paladio de éteres de enol.
Para interceptar las especies de alquilo de paladio generadas en la vía de reacción de Heck.
Para sintetizar aminoacetales a partir de éteres de enol, aminos y alcoholes.

Principales métodos:

Desarrollo de una nueva estrategia sintética que implica la adición nucleofílica a las especies de alquilo de paladio.
Difuncionalización catalizada por el paladio de éteres de enol.
Estudios mecanicistas para elucidar la vía de reacción.

Principales resultados:

Se logró una nueva difuncionalización catalizada por el paladio de éteres enoles con aminos y alcoholes.
Los aminoacetales fueron sintetizados con éxito.
Los estudios mecanicistas identificaron un complejo catiónico ciclometalizado Pd (II) como crucial.

Conclusiones:

La estrategia desarrollada ofrece una nueva ruta a los aminoacetales.
Interceptar los intermediarios alquilo-paladio antes de la inserción migratoria es una estrategia viable.
El complejo catiónico ciclometalizado Pd (II) juega un papel clave en esta transformación.

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