Video Experimental Relacionado

Updated: May 11, 2026

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

Published on: April 1, 2013

Estudios sobre la cicloadición intramolecular areno/aleno de Diels-Alder de Himbert. Estudios mecanicistas y

Yvonne Schmidt¹, Jonathan K Lam, Hung V Pham

¹1102 Natural Sciences II, Department of Chemistry, University of California-Irvine, Irvine, California, 92697-2025, USA.

Journal of the American Chemical Society

|May 3, 2013

Resumen

Los investigadores exploraron el mecanismo de cicloadición de Himbert utilizando métodos computacionales y experimentos. Esta reacción crea eficientemente complejos andamios policíclicos a partir de compuestos tensados.

Área de la Ciencia:

Química orgánica es la química orgánica.
Química computacional es la química computacional.

Sus antecedentes:

La cicloadición intramolecular areno/aleno de Himbert proporciona acceso a compuestos policíclicos tensados.
Estos compuestos son valiosos para sintetizar andamios moleculares complejos.

Objetivo del estudio:

Para dilucidar el mecanismo de reacción de la cicloadición de Himbert.
Para guiar la expansión de su alcance sintético a nuevos sustratos.
Extender la química de la cicloadición a los sistemas carbocíclicos.

Principales métodos:

Se utilizaron métodos computacionales mecánicos cuánticos.
Los experimentos de laboratorio se llevaron a cabo en conjunto con estudios computacionales.

Principales resultados:

Los estudios computacionales sugieren que las adiciones cíclicas proceden a través de vías concertadas.
Se descubrió que un mecanismo biradical gradual era energéticamente desfavorable.
La cicloadición de Himbert se extendió con éxito a los sistemas carbocíclicos.
La guía computacional identificó condiciones de reacción termodinámicamente favorables.

Conclusiones:

La cicloadición de Himbert es un método valioso para construir andamios policíclicos complejos.
Las vías concertadas son favorecidas sobre los mecanismos biradicales.
El alcance de la reacción se ha extendido con éxito a los sistemas carbocíclicos, con la ayuda de predicciones computacionales.

Más Videos Relacionados

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

Published on: September 18, 2016

Videos de Conceptos Relacionados

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.

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.

Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.

Diels–Alder Reaction: Characteristics of Dienes

Diels–Alder Reaction: Characteristics of Dienes

The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...

Cycloaddition Reactions: Overview

Cycloaddition Reactions: Overview

Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.

Diels–Alder Reaction: Characteristics of Dienophiles

Diels–Alder Reaction: Characteristics of Dienophiles

In a Diels–Alder reaction, the diene is usually an electron-rich system and acts as a nucleophile, whereas the dienophile is electron-deficient and functions as an electrophile. Much like the diene, the nature of the dienophile significantly impacts the outcome of the reaction.
Characteristics of Dienophiles
Generally, the best dienophiles are alkenes containing electron-withdrawing substituents such as carbonyl, nitrile, and nitro groups. The feasibility of a Diels–Alder reaction depends on...