Video Experimental Relacionado

Updated: May 12, 2026

Biosynthesis of a Flavonol from a Flavanone by Establishing a One-pot Bienzymatic Cascade

Biosynthesis of a Flavonol from a Flavanone by Establishing a One-pot Bienzymatic Cascade

Published on: August 14, 2019

Síntesis total enantioselectiva en nueve pasos de (-) -vincorina

Benjamin D Horning¹, David W C MacMillan

¹Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, USA.

Journal of the American Chemical Society

|April 17, 2013

Resumen

Se logró una síntesis concisa del alcaloide de akuamilina (-) -vincorina utilizando una cascada de ciclización Diels-Alder, iminium organocatalítica. Este método construye de manera eficiente el complejo núcleo tetraciclico en nueve pasos.

Área de la Ciencia:

Química orgánica es la química orgánica.
Química sintética de la química sintética.
Síntesis de Productos Naturales.

Sus antecedentes:

Los alcaloides de akuamilina son una clase compleja de productos naturales con un interés farmacológico significativo.
La síntesis total de (-) -vincorina presenta un desafío considerable debido a su intrincada estructura tetraciclica.

Objetivo del estudio:

Para lograr una síntesis total concisa y altamente enantioselectiva del alcaloide de akuamilina (-) -vincorina.
Desarrollar una estrategia sintética eficiente para la construcción del complejo núcleo de alcaloides tetraciclicos.

Principales métodos:

Una reacción organocatalítica estereoselectiva de Diels-Alder seguida de una cascada de ciclización del iminio.
Instalación del anillo de azepanilo de siete miembros a través de una ciclización mediada por un solo electrón de un precursor de tellururo de acilo.

Principales resultados:

El núcleo alcalóide tetraciclico de (-) -vincorina fue construido en un solo paso a partir de precursores achirales simples.
La síntesis total se completó en nueve pasos con un rendimiento total del 9%.

Conclusiones:

Se ha desarrollado con éxito una síntesis total altamente eficiente y enantioselectiva de (-) -vincorina.
La estrategia sintética empleada, con una cascada organocatalítica y una reacción de formación de anillos única, ofrece un enfoque valioso para la construcción de alcaloides complejos.

Más Videos Relacionados

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones

Published on: February 7, 2019

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

Videos de Conceptos Relacionados

Regioselective Formation of Enolates

Regioselective Formation of Enolates

As depicted in the figure below, the unsymmetrical ketones can form two possible enolates: less substituted or more substituted enolates. Usually, the thermodynamic enolates are formed from the more substituted α-carbon atom, while the kinetic enolates are formed faster by deprotonation from the less substituted position. The thermodynamic enolates have lower energy, so they are more stable. But the energy required to form kinetic enolates is less.

Synthesis of α-Substituted Carbonyl Compounds: The Stork Enamine Reaction

Synthesis of α-Substituted Carbonyl Compounds: The Stork Enamine Reaction

α-Substituted ketones or aldehydes can be synthesized from enamines by the Stork enamine reaction, named after its pioneer Gilbert Stork. Enamines are useful synthetic intermediates where the lone pair on nitrogen is in conjugation with the C=C bond. They resemble enolate ions, as the resonance forms of both species have a nucleophilic α carbon.

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.

Stereochemical Effects of Enolization

Stereochemical Effects of Enolization

The chiral α-carbon of the carbonyl compound is the stereocenter of the molecule. As shown in the figure below, when such a carbonyl compound undergoes racemization under an acidic or basic condition, an achiral enol is formed.

Alkylation of β-Diester Enolates: Malonic Ester Synthesis

Alkylation of β-Diester Enolates: Malonic Ester Synthesis

Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.