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Cicloadiciones secuenciales [3 + 2]-dipolares sin metales que utilizan cicloctinas y 1,3-dipolos de diferente

Brian C Sanders¹, Frédéric Friscourt, Petr A Ledin

¹Complex Carbohydrate Research Center, and Department of Chemistry, University of Georgia, 315 Riverbend Road, Athens, Georgia 30602, United States.

Journal of the American Chemical Society

|December 25, 2010

Resumen

Este estudio introduce reacciones de clic bioortogonales más rápidas y libres de metales utilizando óxidos de nitrilo y diazocarbonilos con cicloctinas. El nuevo método permite una eficiente funcionalización de una sola olla de biomoléculas y materiales.

Área de la Ciencia:

Química orgánica es la química orgánica.
Biología Química Biología química.
Ciencia de los materiales Ciencia de los materiales.

Sus antecedentes:

Las cicloadiciones libres de metales de cicloactinas y azidas son útiles pero limitadas en velocidad y versatilidad.
Existe la necesidad de reacciones bioortogonales más eficientes para la biología química y la ciencia de los materiales.

Objetivo del estudio:

Para desarrollar reacciones de clic libres de metales más rápidas y versátiles.
Explorar el uso de óxidos de nitrilo y derivados de diazocarbonilo en cicloadiciones con cicloctinas.
Para permitir la funcionalización eficiente de las biomoléculas y materiales.

Principales métodos:

Reacciones de cicloadición 1,3-dipolar entre cicloctinas y óxidos de nitrilo o derivados de diazocarbonilo.
Preparación de óxidos de nitrilo a través de la oxidación directa de oximas utilizando BAIB.
Procedimiento de una sola olla que combina la formación de oximas, la oxidación y la cicloadición.
Funcionalización del centro anómero de los hidratos de carbono.

Principales resultados:

Los óxidos de nitrilo y los derivados de diazocarbonilo se someten fácilmente a cicloadiciones 1,3-dipolares con las cicloctinas.
Las cicloadiciones con óxidos de nitrilo son significativamente más rápidas que las con azidas.
Se estableció un procedimiento de una sola olla para la generación de óxido de nitrilo y la cicloadición.
La metodología se aplicó con éxito para funcionalizar los carbohidratos con varias etiquetas.

Conclusiones:

Las cicloadiciones óxido de nitrilo-alquina ofrecen una alternativa más rápida a las cicloadiciones azida-alquina para la química bioortogonal.
Las oximas y azidas sirven como un par ortogonal para reacciones secuenciales de clics libres de metales.
Este enfoque permite la multifuncionalización de biomoléculas y materiales sin catalizadores de metales tóxicos.

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