Reducción de amida retorcida bajo condiciones de Wolff-Kishner: síntesis de un derivado del benzo-1-aza-adamantano

Video Experimental Relacionado

Updated: Jul 13, 2026

Synthesis of 1,2-Azaborines and the Preparation of Their Protein Complexes with T4 Lysozyme Mutants

Synthesis of 1,2-Azaborines and the Preparation of Their Protein Complexes with T4 Lysozyme Mutants

Published on: March 25, 2017

Crystal G Bashore¹, Ivan J Samardjiev, Jon Bordner

¹Pfizer Global Research and Development, Groton Laboratories, Pfizer Inc., Groton, CT 06340, USA.

Journal of the American Chemical Society

|March 13, 2003

Resumen

Los investigadores sintetizaron un derivado del benzo-1-aza-adamantano utilizando una nueva reducción de Wolff-Kishner de una amida "torcida". Este método eficiente de un solo frasco produce el compuesto objetivo sin hidrólisis no deseada, mostrando una nueva aplicación sintética.

Área de la Ciencia:

Química orgánica es la química orgánica.
Metodología sintética de la metodología sintética.
Química Heterocíclica La Química Heterocíclica es una de las más conocidas.

Sus antecedentes:

Los derivados del benzo-1-aza-adamantano son estructuras policíclicas complejas.
La reducción de Wolff-Kishner es un método estándar para convertir carbonilos en grupos metileno.
La aplicación de la reducción de Wolff-Kishner a las amidas no estabilizadas es un reto.

Objetivo del estudio:

Para sintetizar el derivado benzo-1-aza-triciclo[4.3.1.1(3,8) ]decaneado (1). para sintetizar el derivado benzo-1-aza-triciclo[4.3.1.1(3,8) ]decaneado (1).
Explorar una nueva aplicación de la reducción de Wolff-Kishner en una amida "torcida".
Desarrollar una ruta sintética eficiente y de alto rendimiento.

Principales métodos:

Síntesis de un amino éster clave intermedio.
Conversión del amino éster en una amida "torcida".
Aplicación de las condiciones de reducción de Wolff-Kishner (hidrazina, KOH/etilenglicol) a la amida.

Principales resultados:

Síntesis exitosa del intermediario "torcido" de aminohidrazona.
Reducción eficiente de la amida "torcida" al compuesto objetivo 1 bajo condiciones de Wolff-Kishner.
El alto rendimiento se logra en un conveniente procedimiento de un solo frasco sin hidrólisis.

Conclusiones:

Se ha demostrado una nueva aplicación de la reducción de Wolff-Kishner para amidas "torcidas".
El método descrito proporciona una ruta eficiente a los derivados del benzo-1-aza-adamantano.
Esta estrategia sintética ofrece una herramienta valiosa para la construcción de andamios heterocíclicos complejos.

Más Videos Relacionados

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines

Published on: January 3, 2018

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles

Published on: August 22, 2018

Videos de Conceptos Relacionados

Aldehydes and Ketones to Alkanes: Wolff–Kishner Reduction

Aldehydes and Ketones to Alkanes: Wolff–Kishner Reduction

Wolff–Kishner reduction involves converting aldehydes and ketones to alkanes using hydrazine and a base. The reaction converts a carbonyl group to a methylene group. The method was independently discovered by N. Kishner in 1911 and L. Wolff in 1912. The reduction is carried out in high-boiling solvents such as ethylene glycol and diethylene glycol because heat is required to deprotonate the N–H proton in one of the reaction steps.

Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism

Benzene to 1,4-Cyclohexadiene: Birch Reduction Mechanism

Birch reduction uses solvated electrons as reducing agents. The reaction converts benzene to 1,4-cyclohexadiene. The reaction proceeds by the transfer of a single electron to the ring to form a benzene radical anion. This anion is highly basic—it abstracts a proton from the alcohol to form a cyclohexadienyl radical. Another single electron transfer gives the cyclohexadienyl anion. A proton transfer from the alcohol forms 1,4-cyclohexadiene. Since this reduction occurs via radical anion...

Preparation of 1° Amines: Azide Synthesis

Preparation of 1° Amines: Azide Synthesis

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...

Preparation of Amines: Reduction of Oximes and Nitro Compounds

Preparation of Amines: Reduction of Oximes and Nitro Compounds

Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and aromatic nitro compounds to primary amines takes place by either catalytic hydrogenation or by using active metals like Fe, Zn, and Sn in the presence of an acid.
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...

Preparation of Amines: Reductive Amination of Aldehydes and Ketones

Preparation of Amines: Reductive Amination of Aldehydes and Ketones

Carbonyl compounds and primary amines undergo reductive amination first to produce imines, followed by secondary amines in the same reaction mixture, using selective reducing agents like sodium cyanoborohydride or sodium triacetoxyborohydride. Reductive amination produces different degrees of substitution of amines depending on the starting amine substrate.

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

Diazonium 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...