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Síntesis de heterociclos catalizados por rodio (III) utilizando un oxidante interno: mejora de la reactividad y

Nicolas Guimond¹, Serge I Gorelsky, Keith Fagnou

¹Centre for Catalysis Research and Innovation, Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada. nguim025@uottawa.ca

Journal of the American Chemical Society

|April 2, 2011

Resumen

Los investigadores desarrollaron un nuevo oxidante interno / grupo directivo para la síntesis de isoquinolona catalizada por el rodio (III). Este avance permite reacciones a temperatura ambiente con bajas cargas de catalizador y el uso de alquinas o alquenos terminales.

Área de la Ciencia:

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

Sus antecedentes:

Los oxidantes/grupos directores internos mejoran la funcionalización C-H catalizada por metales en la síntesis de heterociclos.
Los métodos anteriores para la síntesis de isoquinolonas catalizados por rodio (III) eran redox-neutrales y de alcance limitado para sustratos.

Objetivo del estudio:

Desarrollar un grupo oxidante/director interno más reactivo para la síntesis de isoquinolona catalizada por el rodio.
Para permitir reacciones a temperatura ambiente con bajas cargas de catalizador y ampliar el alcance del sustrato para incluir alquinas terminales.

Principales métodos:

Reacciones catalizadas por el rodio (III) utilizando un nuevo grupo oxidante/director interno.
Exploración de las reacciones con alcinos y alquenos terminales (incluido el etileno).
Investigaciones mecanicistas que incluyen estudios experimentales y cálculos de la Teoría Funcional de Densidad (DFT).

Principales resultados:

Síntesis exitosa de una amplia variedad de isoquinolonas a temperatura ambiente utilizando bajas cargas de catalizador (0,5 mol %).
Demostración por primera vez del uso de alquinas terminales en la síntesis de heterociclos catalizados por el rodio ((III) oxidativo.
Formación a temperatura ambiente de 3,4-dihidroisoquinolonas utilizando alquenos, incluido el etileno.

Conclusiones:

El nuevo grupo oxidante/director interno mejora significativamente la reactividad y amplía el alcance del sustrato para la síntesis de isoquinolonas catalizadas por rodio (III).
Los estudios mecánicos sugieren un cambio en el paso de limitación de la rotación a la desmetalización-deprotonación concertada (CMD) y apoyan una eliminación reductora gradual de enlaces C-N / ruta de adición oxidativa de enlaces N-O.

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