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Transposiciones de 1,2-redóxicas de las amidas terciarias

Benjamin D A Shennan¹, Sergio Sánchez-Alonso¹, Gabriele Rossini¹

¹Department of Chemistry, University of Oxford, Chemical Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, U.K.

Journal of the American Chemical Society

|September 27, 2023

Resumen

Este estudio introduce un nuevo método para alterar la reactividad molecular mediante la transposición de los niveles de oxidación del átomo de carbono en las amidas terciarias. Esto permite la síntesis eficiente de un solo recipiente de valiosos compuestos aminos oxigenados para otras aplicaciones químicas.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

La alteración de los estados de oxidación de los átomos de carbono adyacentes es clave para modificar la reactividad molecular.
Las amidas terciarias son motivos estructurales comunes con potencial para diversas transformaciones químicas.

Objetivo del estudio:

Desarrollar un método para la transposición de los niveles de oxidación del átomo de carbono en las amidas terciarias.
Para lograr la síntesis de una sola olla de aminas terciarias oxigenadas 1,2- y 1,3.
Explorar la utilidad de esta estrategia de transposición redox para la síntesis de productos intermedios valiosos.

Principales métodos:

Reducción catalizada por iridio de las amidas terciarias.
Funcionalización de los intermediarios de enamina formados transitoriamente.
Desarrollo de nuevas reacciones de transposición de 1,2-carbonilo.

Principales resultados:

Transposición exitosa de los niveles de oxidación en amidas terciarias cíclicas y acíclicas.
Síntesis de una sola vasija de aminas terciarias oxigenadas 1,2- y 1,3.
Síntesis demostrada de aminoalcoholes y enaminonas.
Se generan diversos productos de aminas β-funcionalizadas.

Conclusiones:

La estrategia de transposición redox desarrollada proporciona una herramienta poderosa para sintetizar derivados de aminas complejas.
Las aminas β-funcionalizadas resultantes son intermediarios versátiles para acceder a moléculas biológicamente relevantes.
Esta metodología expande la utilidad sintética de las amidas terciarias a través de la manipulación controlada del nivel de oxidación.

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