Video Experimental Relacionado

Updated: Jul 18, 2025

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

Aminodealquenilación: la ozonolización y la catálisis del cobre convierten los enlaces C (sp3) -C (sp2) en enlaces C

Zhiqi He¹, Jose Antonio Moreno¹, Manisha Swain¹

¹Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095-1569, USA.

Science (New York, N.Y.)

|August 24, 2023

Resumen

Este estudio introduce un nuevo método para la funcionalización de enlaces sigma C(sp3) -C(sp2) utilizando ozonolización y catálisis de cobre. Este avance permite la síntesis de nuevos enlaces C ((sp3) -N, valiosos en la química medicinal y la ciencia de los materiales.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

La aminación del enlace π alqueno está bien establecida.
La funcionalización de los enlaces adyacentes C ((sp3) -C ((sp2) σ es significativamente menos explorada.
Se necesitan nuevos métodos para la formación eficiente de enlaces C-N en estas posiciones.

Objetivo del estudio:

Desarrollar un nuevo método para el acoplamiento cruzado de ruptura de enlaces C ((sp3) - C ((sp2)).
Para permitir la construcción de nuevos enlaces de C ((sp3) -N en condiciones suaves.
Demostrar la utilidad de esta transformación en la funcionalización de última etapa y en la síntesis de productos naturales.

Principales métodos:

Ozonólisis combinada con catálisis de cobre.
Condiciones de reacción leves.
Reacciones de acoplamiento cruzado que implican la escisión del enlace σ C ((sp3) -C ((sp2).

Principales resultados:

Construcción exitosa de nuevos enlaces C ((sp3) -N.
Modificación tardía de las hormonas, reactivos farmacéuticos, péptidos y nucleósidos.
Síntesis de alcaloides terpenoides artificiales y de aminas quirales complejas a partir de terpenos.
Metilación directa de nucleósidos mediante el uso de α-metilestireno.

Conclusiones:

El método desarrollado ofrece una ruta no convencional para la funcionalización del enlace σ C ((sp3) - C ((sp2).
La transformación es versátil y aplicable a diversos andamios moleculares.
Los estudios mecánicos sugieren un proceso cooperativo de pares de iones de cobre.

Más Videos Relacionados

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

Published on: November 21, 2017

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

Published on: May 26, 2019

Videos de Conceptos Relacionados

Oxidative Cleavage of Alkenes: Ozonolysis

Oxidative Cleavage of Alkenes: Ozonolysis

In ozonolysis, ozone is used to cleave a carbon–carbon double bond to form aldehydes and ketones, or carboxylic acids, depending on the work-up.
Ozone is a symmetrical bent molecule stabilized by a resonance structure.

Alkynes to Carboxylic Acids: Oxidative Cleavage

Alkynes to Carboxylic Acids: Oxidative Cleavage

Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions...

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.

Acid-Catalyzed α-Halogenation of Aldehydes and Ketones

Acid-Catalyzed α-Halogenation of Aldehydes and Ketones

By replacing an α-hydrogen with a halogen, acid-catalyzed α-halogenation of aldehydes or ketones yields a monohalogenated product
In the first step of the mechanism, the acid protonates the carbonyl oxygen resulting in a resonance-stabilized cation, which subsequently loses an α-hydrogen to form an enol tautomer. The C=C bond in an enol is highly nucleophilic because of the electron-donating nature of the –OH group. Consequently, the double bond attacks an electrophilic halogen to form a...

Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes

Preparation of Aldehydes and Ketones from Alcohols, Alkenes, and Alkynes

Aldehydes and ketones are prepared from alcohols, alkenes, and alkynes via different reaction pathways. Alcohols are the most commonly used substrates for synthesizing aldehydes and ketones. The conversion of alcohol to aldehyde, which involves the oxidation process, depends on the class of the alcohol used and the strength of the oxidizing agent. For instance, primary alcohol will form an aldehyde when treated with a weak oxidizing agent; however, it gets over-oxidized to a carboxylic acid in...