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Reducción altamente quimioselectiva de amidas (primarias, secundarias, terciarias) a alcoholes utilizando
Michal Szostak1, Malcolm Spain, Andrew J Eberhart
1School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.
Journal of the American Chemical Society
|January 28, 2014
Resumen
Un nuevo método reduce directamente las amidas a los alcoholes utilizando samario (II) yoduro (SmI2), amina y agua. Esta reducción quimio-selectiva favorece la escisión de los enlaces C-N, produciendo alcoholes en grandes cantidades con una amplia tolerancia de grupo funcional.
Área de la Ciencia:
- Química orgánica es la química orgánica.
- Química sintética de la química sintética.
- La catálisis de la catálisis.
Sus antecedentes:
- La reducción de amida generalmente implica condiciones difíciles o reactivos complejos.
- La escisión selectiva de enlaces C-N en amidas es un desafío.
- Los métodos existentes a menudo conducen a productos de escisión de C-O no deseados.
Objetivo del estudio:
- Desarrollar un método altamente quimioselectivo para la reducción directa de amida a alcohol.
- Para investigar el mecanismo que controla el C-N versus el C-O en la escisión de bonos.
- Para explorar la generación de radicales de tipo acilo a partir de amidas.
Principales métodos:
- Reducción directa de amidas primarias, secundarias y terciarias.
- Utilizado samario (II) yoduro (SmI2) en combinación con una amina y agua.
- Se ha investigado la selectividad de reacción y la tolerancia del grupo funcional.
- Realizó estudios mecanicistas que involucran transferencia de electrones y coordinación intermedia.
Principales resultados:
- Se logró una reducción altamente quimioselectiva de amidas a alcoholes.
- Se observó una escisión exclusiva de enlaces C-N, evitando los productos de escisión de C-O.
- Demostró excelentes rendimientos y una amplia tolerancia al grupo funcional.
- Se ha informado de acceso directo a los radicales de tipo acilo a partir de amidas no activadas.
Conclusiones:
- El sistema SmI2/amina/H2O proporciona una ruta novedosa y eficiente para la reducción de amidas a alcoholes.
- El mecanismo de reacción implica la coordinación Sm y la transferencia de electrones, controlando la selectividad C-N/C-O.
- Este método ofrece una vía leve y directa para la generación de radicales de tipo acilo.
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