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La funcionalización C-H enantioselectiva catalizada por el rodio (II) de los indoles

Andrew DeAngelis¹, Valerie W Shurtleff, Olga Dmitrenko

¹Brown Laboratories, Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States.

Journal of the American Chemical Society

|January 27, 2011

Resumen

Los investigadores desarrollaron un nuevo método catalítico para la funcionalización C-H de los indoles utilizando compuestos diazo. Este proceso enantioselectivo produce α-alquilo-α-indolilacetatos con alta eficiencia y selectividad.

Área de la Ciencia:

Química orgánica es la química orgánica.
La catálisis es la catálisis.
Síntesis asimétrica de síntesis.

Sus antecedentes:

La funcionalización C-H es una transformación clave en la síntesis orgánica.
Los indoles son importantes compuestos heterocíclicos con diversas actividades biológicas.
La síntesis enantioselectiva es crucial para desarrollar fármacos y materiales quirales.

Objetivo del estudio:

Desarrollar un método catalítico y enantioselectivo para la funcionalización directa C-H de los indoles.
Para utilizar compuestos diazo como precursores de carbenos para la modificación del indole.
Para lograr altos rendimientos y enantioselectividades en los productos de funcionalización.

Principales métodos:

Empleando un catalizador quiral de rodio, Rh(2)(S-NTTL)(4).
Reaccionan los α-alquilo-α-diazoesters con los indoles.
Utilizando la activación C-H en la posición C ((3) de los indolos.

Principales resultados:

Se logró una exitosa funcionalización catalítica enantioselectiva C-H de los indoles.
Los α-alquilo-α-indolilacetatos fueron sintetizados en altos rendimientos y enantioselectividades.
Los cálculos de la Teoría Funcional de Densidad (DFT) apoyaron un mecanismo propuesto que involucra un intermediario Rh-ilido.

Conclusiones:

Se ha establecido un método novedoso y eficiente para la funcionalización enantioselectiva del indole C-H.
El método desarrollado ofrece una valiosa ruta a los α-alquilo-α-indolilacetatos quirales.
El mecanismo propuesto proporciona una visión mecánica del ciclo catalítico.

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