Video Experimental Relacionado

Updated: Dec 11, 2025

Preparation of Enantiopure Non-Activated Aziridines and Synthesis of Biemamide B, D, and epiallo-Isomuscarine

Preparation of Enantiopure Non-Activated Aziridines and Synthesis of Biemamide B, D, and epiallo-Isomuscarine

Published on: June 13, 2022

Síntesis total de las dapnezominas A y B

Guangpeng Xu^1,2, Jinbao Wu², Luyang Li²

¹College of Life Sciences, Beijing Normal University, Beijing, 100875, China.

Journal of the American Chemical Society

|August 20, 2020

Resumen

Los investigadores lograron la primera síntesis total de las dapnezominas A y B, productos naturales complejos que presentan un núcleo único de aza-adamantano. Esta síntesis modular utilizó un material inicial de terpenos quirales y estrategias de reacción avanzadas en solo 14 pasos.

Área de la Ciencia:

Química orgánica
Síntesis de productos naturales
Química medicinal

Sus antecedentes:

Las Daphnizominas A y B son alcaloides de Daphniphyllum estructuralmente únicos.
Estos alcaloides poseen un esqueleto de núcleo de aza-adamantano distintivo.
La síntesis de estos productos naturales complejos presenta desafíos significativos.

Objetivo del estudio:

Desarrollar una estrategia sintética modular para las daphnezominas A y B.
Para lograr la primera síntesis total de estos alcaloides inusuales.
Explorar diversas metodologías de reacción para la construcción del núcleo de aza-adamantano.

Principales métodos:

Utilizó un terpeno quiral, (S) -carvone, como el material de partida.
Empleó la aminación alilica Sharpless y la ciclización oxidativa catalizada por el paladio para formar la columna vertebral azabiciclo[3.3.1]nonano.
Aplicación de acoplamiento estereoselectivo B-alquilo Suzuki-Miyaura y transferencia de átomos de hidrógeno mediada por Fe (HAT) para la construcción de centros estereoscópicos.
Incorporó una estrategia de bloqueo epímero para ensamblar el núcleo aza-adamantano.

Principales resultados:

Sintetizó con éxito la columna vertebral azabiciclo [3.3.1] nonano de (S) -carvone.
Estableció los estereocentros C6 y C8 utilizando técnicas avanzadas de acoplamiento y ciclización radical.
Construido el núcleo de aza-adamantano altamente congestionado a través de una estrategia de bloqueo de epímero.
Se logró la primera síntesis total de (-) -daphnezomines A y B en una secuencia concisa de 14 pasos.

Conclusiones:

El enfoque modular presentado proporciona una ruta eficiente a las daphnezominas A y B.
Esta síntesis pone de relieve la utilidad de diversas estrategias de reacción en la construcción de marcos complejos de alcaloides.
La metodología ofrece una plataforma para acceder a productos naturales y análogos estructuralmente relacionados.

Más Videos Relacionados

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

A Direct, Early Stage Guanidinylation Protocol for the Synthesis of Complex Aminoguanidine-containing Natural Products

A Direct, Early Stage Guanidinylation Protocol for the Synthesis of Complex Aminoguanidine-containing Natural Products

Published on: September 9, 2016

Videos de Conceptos Relacionados

Aryldiazonium Salts to Azo Dyes: Diazo Coupling

Aryldiazonium Salts to Azo Dyes: Diazo Coupling

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...

Adrenergic Agonists: Chemistry and Structure-Activity Relationship

Adrenergic Agonists: Chemistry and Structure-Activity Relationship

Adrenergic agonists' structure-activity relationship (SAR) determines their selectivity and efficacy. These agonists comprise a phenylethylamine moiety with an aromatic ring and an ethylamine side chain.
Aromatic ring substitutions: Substituting the aromatic ring with –OH groups at positions 3 and 4 yields catecholamines (e.g., epinephrine), which have a high affinity for adrenoceptors. Hydrogen bonding between –OH groups and receptors enhances adrenergic activity.
Separation of...

Preparation of 1° Amines: Gabriel Synthesis

Preparation of 1° Amines: Gabriel Synthesis

Direct alkylation is not a suitable method for synthesizing amines because it produces polyalkylated products. Gabriel synthesis is the most preferred method to exclusively make primary amines. The method uses phthalimide, which contains a protected form of nitrogen that participates in alkylation only once to predominantly give primary amines.
Strong bases like NaOH or KOH deprotonate the phthalimide to form the corresponding anion, which acts as a nucleophile. Further, the anion attacks an...

Carboxylic Acids to Methylesters: Alkylation using Diazomethane

Carboxylic Acids to Methylesters: Alkylation using Diazomethane

Carboxylic acids react with diazomethane in an ether solvent via alkylation at the carboxylate oxygen atom to give methyl esters of the corresponding acid with excellent yields.

Diazonium Group Substitution: –OH and –H

Diazonium 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.

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...