Video Experimental Relacionado

Updated: Mar 8, 2026

Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions

Synthesis of a Borylated Ibuprofen Derivative Through Suzuki Cross-Coupling and Alkene Boracarboxylation Reactions

Published on: November 30, 2022

Arilación altamente para selectiva controlada por amida y ligando de arenas simples monosubstituidas con ácidos

Yu-Xin Luan¹, Tao Zhang¹, Wei-Wei Yao¹

¹State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University , Tianjin 300071, China.

Journal of the American Chemical Society

|January 24, 2017

Resumen

Las nuevas reacciones catalizadas por paladio permiten arilaciones altamente para-selectivas de arenas simples utilizando ácidos arilborónicos. Los ligandos de amida, en particular el DMF, son clave para controlar la selectividad en la formación de compuestos biarílicos.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

Los compuestos de biarylo son frecuentes en los productos farmacéuticos y la ciencia de los materiales.
Las relaciones selectivas anteriores a menudo requerían grupos dirigidos o condiciones duras.
El desarrollo de métodos eficientes para la síntesis para-selectiva de biarilo sigue siendo un desafío.

Objetivo del estudio:

Desarrollar un método catalizado por el paladio para la arilación altamente para selectiva de arenes monosubstituidos.
Identificar los factores clave que controlan la selectividad en esta transformación.
Para sintetizar estructuras de biarilo ampliamente existentes de manera eficiente.

Principales métodos:

Reacciones de acoplamiento cruzado catalizadas por el paladio.
Utilizando ácidos arilborónicos como socios de acoplamiento.
El uso de ligandos de amida, específicamente N,N-dimetilformamida (DMF), para el control de la selectividad.

Principales resultados:

Se logra una alta para-selectividad en la arilación de arenas simples monosubstituidas.
Demostró el papel crítico de los ligandos de amida, especialmente el DMF, en la dirección de la selectividad.
Ha sintetizado con éxito varios compuestos biarílicos.

Conclusiones:

Se ha establecido un nuevo y eficiente método de arilación para selectiva catalizada por Pd.
Los ligandos de amida son cruciales para lograr una alta selectividad en estas relaciones.
Esta metodología proporciona una ruta valiosa a las estructuras biarílicas importantes.

Más Videos Relacionados

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

Published on: February 16, 2020

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Published on: July 30, 2017

Videos de Conceptos Relacionados

Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)

Nucleophilic Aromatic Substitution: Addition–Elimination (S_NAr)

Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...

Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1

Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic S_N1

Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...

ortho–para-Directing Activators: –CH3, –OH, –&NoBreak;NH2, –OCH3

ortho–para-Directing Activators: –CH₃, –OH, –⁠NH₂, –OCH₃

All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...

Nucleophilic Aromatic Substitution: Elimination–Addition

Nucleophilic Aromatic Substitution: Elimination–Addition

Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...

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 stereochemistry.

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.