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Un estudio mecanicista comparativo de las reacciones de acoplamiento oxidativo catalizadas por Cu con

Esther Boess¹, Corinna Schmitz, Martin Klussmann

¹Max-Planck-Institut fuer Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Muelheim an der Ruhr, Germany.

Journal of the American Chemical Society

|February 18, 2012

Resumen

Este estudio compara dos métodos de acoplamiento catalizado por cobre. El método aeróbico utiliza un intermediario de iones de iminio, mientras que el método de hidroperoxido de tert-butilo (TBHP) implica un intermediario de peróxido alfa-amino.

Área de la Ciencia:

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

Sus antecedentes:

Las reacciones de acoplamiento oxidativo catalizadas por el cobre son vitales en la síntesis orgánica.
Comprender los mecanismos de reacción es crucial para optimizar las rutas sintéticas.

Objetivo del estudio:

Para investigar comparativamente los mecanismos de dos reacciones de acoplamiento oxidativo catalizadas por Cu.
Para aclarar el papel de los intermediarios en las reacciones que involucran N-feniltetrahidroisoquinolina.

Principales métodos:

Estudio mecanicista comparativo del acoplamiento oxidativo catalizado por Cu.
Se utilizaron dos sistemas catalíticos: CuCl2·2H2O/O2 y CuBr/tert-butilo hidroperoxido (TBHP).
Realizó estudios sintéticos con varios nucleófilos para sondear la reactividad intermedia.

Principales resultados:

Se identificaron los principales intermediarios para ambos sistemas catalíticos.
El método aeróbico procede a través de un intermediario de iones de iminio oxidado con cobre.
El sistema CuBr/TBHP incluye un intermediario de peróxido alfa-amino, que precede al ion iminio.

Conclusiones:

Se revelaron diferencias mecánicas entre las reacciones de acoplamiento aeróbico y las mediadas por TBHP.
Destacó los distintos roles de oxígeno y TBHP en los ciclos catalíticos.
Proporcionó información sobre la electrophilicidad del intermedio de iones de iminio basado en la reactividad de los nucleófilos.

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