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Conversión de azidas en compuestos diazo en agua
Ho-Hsuan Chou1, Ronald T Raines
1Department of Chemistry and ∥Department of Biochemistry, University of Wisconsin-Madison , Madison, Wisconsin 53706, United States.
Journal of the American Chemical Society
|September 24, 2013
Resumen
Desarrollamos un nuevo fosfinoester para convertir eficientemente azidas en compuestos diazo bajo condiciones suaves. Este método ofrece altos rendimientos y una amplia tolerancia al grupo funcional, expandiendo las aplicaciones de los compuestos diazo en biología química.
Área de la Ciencia:
- Química orgánica sintética y orgánica.
- Biología química Biología química.
- Química de la bioconjugación en la bioconjugación.
Sus antecedentes:
- Los compuestos diazo son reactivos sintéticos versátiles.
- Su aplicación en biología química sigue siendo limitada.
- Las azidas se incorporan fácilmente a las biomoléculas.
Objetivo del estudio:
- Desarrollar un nuevo método para generar compuestos diazo de azidas.
- Para lograr una formación eficiente de compuestos diazo bajo condiciones suaves y biológicamente relevantes.
- Explorar nuevas vías para la utilización de la química diazo en la biología química.
Principales métodos:
- Diseño y síntesis de un reactivo de fosfinoestero.
- Optimización de las condiciones de reacción (pH, temperatura, amortiguador).
- Evaluación del rendimiento de la reacción y la compatibilidad del grupo funcional.
- Monitoreo colorimétrico del progreso de la reacción.
Principales resultados:
- El fosfinoester convierte eficientemente azidas en compuestos diazo en el amortiguador de fosfato a pH neutro y temperatura ambiente.
- Se lograron altos rendimientos con tolerancia a grupos funcionales nucleófilos y electrófilos comunes.
- El progreso de la reacción fue monitoreado con éxito utilizando colorimetría.
- Potencial demostrado para la modificación de biopolímeros.
Conclusiones:
- Se ha establecido un método novedoso, eficiente y suave para la generación de compuestos diazo de azidas.
- Esta reacción mediada por el fosfinoestero expande la utilidad de las azidas en la biología química.
- El método es adecuado para la funcionalización de biopolímeros y ligandos, abriendo nuevas vías de investigación.
Videos de Conceptos Relacionados
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The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the para position.
01:371° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
01:19Diazonium Group Substitution: –OH and –H
Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
01:20Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
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Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
01:14Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo, or cyano...
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