Video Experimental Relacionado
Updated: May 27, 2026
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
11:44
Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Leves y eficientes reacciones de Heck catalizadas por níquel con olefinas ricas en electrones
Thomas M Gøgsig1, Jonatan Kleimark, Sten O Nilsson Lill
1The Center for Insoluble Protein Structures (inSPIN), Department of Chemistry and the Interdisciplinary Nanoscience Center, Aarhus University, Langelandsgade 140, 8000 Aarhus, Denmark.
Journal of the American Chemical Society
|December 1, 2011
Resumen
Una nueva reacción de Heck catalizada por níquel ofrece una alternativa sostenible para la olefinación de triflato de arilo. Este método utiliza condiciones suaves y logra altos rendimientos, demostrando una amplia compatibilidad con el sustrato y tolerancia al grupo funcional.
Área de la Ciencia:
- Química orgánica es la química orgánica.
- La catálisis de la catálisis.
- Química Sostenible y Sustentable.
Sus antecedentes:
- La reacción de Heck es una piedra angular de la formación de enlaces C-C.
- Los catalizadores de paladio son ampliamente utilizados, pero pueden ser caros y tóxicos.
- El desarrollo de sistemas catalíticos alternativos, rentables y sostenibles es crucial.
Objetivo del estudio:
- Presentar un eficiente protocolo catalizado por níquel para la reacción de Heck de triflados de arilo con éteres de vinilo.
- Establecer una alternativa práctica y más sostenible a los métodos catalizados con paladio.
- Explorar el alcance y las limitaciones de este nuevo sistema catalítico basado en níquel.
Principales métodos:
- Utilizó un sistema catalítico de Ni (COD) 2 y 1,1'-bis (difenilfosfino) ferroceno (DPPF) con Cy2NMe como base.
- Investigó la reacción con una amplia gama de triflados de arilo deficientes en electrones y ricos en electrones.
- Realizó cálculos DFT para dilucidar el mecanismo de reacción.
Principales resultados:
- Se logró una olefinación eficiente de varios triflados de arilo en condiciones suaves.
- Se obtienen altos rendimientos de cetonas de arilo metilo después de la hidrólisis, lo que demuestra un amplio alcance del sustrato.
- Se ha demostrado una buena tolerancia del grupo funcional, comparable a las reacciones de Heck catalizadas por el paladio.
- Los cálculos de DFT sugieren una vía favorable que involucra un intermediario catiónico de níquel (II).
Conclusiones:
- El protocolo catalizado por níquel desarrollado es una alternativa práctica y sostenible para la arilación regioselectiva de éteres de vinilo.
- El sistema catalítico exhibe una alta actividad y una amplia aplicabilidad para la síntesis de valiosos compuestos orgánicos.
- Los conocimientos mecanicistas proporcionan una base para una mayor optimización y desarrollo de reacciones de acoplamiento cruzado catalizadas por níquel.
Videos de Conceptos Relacionados
02:17Reduction 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...
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...
02:50Catalysis
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
02:24Reduction 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.
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.
02:04Oxidation 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.
01:13Olefin Metathesis Polymerization: Overview
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
02:13Reduction of Alkenes: Catalytic Hydrogenation
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...