Video Experimental Relacionado

Updated: Aug 28, 2025

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Published on: June 20, 2014

Hidroxilación de C-H habilitada por ligandos con H acuoso a temperatura ambiente

Zhen Li¹, Han Seul Park¹, Jennifer X Qiao²

¹The Scripps Research Institute, 10550 N. Torrey Pines Road, La Jolla, California 92037, United States.

Journal of the American Chemical Society

|September 22, 2022

Resumen

Los investigadores desarrollaron un nuevo catalizador para la hidroxilación C-H a temperatura ambiente utilizando peróxido de hidrógeno verde. Este método escalable convierte eficientemente los ácidos benzoicos y fenilacéticos, lo que permite la síntesis de moléculas complejas como el ibuprofeno y los productos naturales.

Área de la Ciencia:

Catálisis
Química orgánica
Química ecológica

Sus antecedentes:

Las reacciones de activación de C-H catalizadas por Palladium (II) son frecuentes, sin embargo, el desarrollo de catalizadores compatibles con oxidantes verdes como el peróxido de hidrógeno acuoso sigue siendo un desafío significativo.
La compatibilidad de los catalizadores de paladio con los oxidantes sostenibles, en particular el peróxido de hidrógeno acuoso, ha sido un obstáculo persistente en varias oxidaciones catalíticas, incluidas las reacciones de tipo Wacker.

Objetivo del estudio:

Desarrollar un nuevo sistema catalítico para la hidroxilación eficiente de C-H utilizando un oxidante verde.
Para permitir la hidroxilación C-H catalizada por el paladio a temperatura ambiente de los ácidos benzoico y fenilacético utilizando peróxido de hidrógeno acuoso.
Demostrar la escalabilidad y la utilidad de la metodología desarrollada para sintetizar compuestos valiosos.

Principales métodos:

Desarrollo de un ligando bifuncional de carboxilpiridona (CarboxPyridone).
Se utiliza el peróxido de hidrógeno acuoso (35% H₂ O₂) como oxidante compatible con la industria.
Reacciones de hidroxilación C-H catalizadas por el paladio a temperatura ambiente.

Principales resultados:

El ligando CarboxPyridone permitió la hidroxilación C-H a temperatura ambiente de una amplia gama de ácidos benzoicos y fenilacéticos.
Escalabilidad demostrada con una síntesis a escala de 1000 mmol de ibuprofeno (206 g) utilizando sólo 1 mol% de carga del catalizador de paladio.
Demostró la utilidad del protocolo a través de la derivación de productos y la síntesis de productos naturales polifluorados (cumestán, pterocarpeno) a partir de productos intermedios del fenol.

Conclusiones:

Un nuevo ligando de CarboxPyridone facilita una hidroxilación C-H catalizada por paladio eficiente y escalable utilizando peróxido de hidrógeno acuoso a temperatura ambiente.
Esta metodología ofrece un enfoque práctico y ecológico para sintetizar moléculas orgánicas valiosas, incluidos productos farmacéuticos y naturales.
El sistema catalítico desarrollado supera las limitaciones anteriores en el uso de oxidantes sostenibles con catalizadores de paladio.

Más Videos Relacionados

Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes

Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes

Published on: June 24, 2022

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

Published on: April 12, 2019

Videos de Conceptos Relacionados

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...

Acid Halides to Carboxylic Acids: Hydrolysis

Acid Halides to Carboxylic Acids: Hydrolysis

Hydrolysis of acid halides is a nucleophilic acyl substitution reaction in which acid halides react with water to give carboxylic acids. The reaction occurs readily and does not require acid or a base catalyst.
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields carboxylic...

Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration

Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration

The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.

Regioselectivity and Stereochemistry of Hydroboration

Regioselectivity and Stereochemistry of Hydroboration

A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.