Video Experimental Relacionado
Updated: Jun 10, 2026
12:27
Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
Cianización de arenas a través de la borilación catalizada por iridio
Carl W Liskey1, Xuebin Liao, John F Hartwig
1Department of Chemistry, University of Illinois, 600 South Matthews Avenue, Urbana, Illinois 61801-3602, USA.
Journal of the American Chemical Society
|August 4, 2010
Resumen
Este estudio introduce un método de una sola olla para la meta cianuración de arenas utilizando borilación C-H catalizada por iridio y cianuración mediada por cobre. Este eficiente proceso sintetiza nitriles de arilo meta-sustituidos a partir de diversos compuestos aromáticos.
Área de la Ciencia:
- Química orgánica es la química orgánica.
- La catálisis de la catálisis.
- Metodología sintética de la metodología sintética.
Sus antecedentes:
- Los nitriles de arilo son bloques de construcción cruciales en los productos farmacéuticos y la ciencia de los materiales.
- Dirigir la funcionalización a la meta-posición de las arenas sigue siendo un desafío sintético.
- Los métodos existentes para la metacianización a menudo requieren procedimientos en varios pasos o condiciones duras.
Objetivo del estudio:
- Desarrollar un novedoso método de una sola olla para la meta cianuración de arenas.
- Establecer condiciones eficientes para la cianuración mediada por cobre de ésteres y ácidos de arilboronato.
- Demostrar la amplia aplicabilidad de la metodología desarrollada para sintetizar nitriles de arilo meta-sustituidos.
Principales métodos:
- Una borilación secuencial de un potencial de C-H catalizada por iridio de las arenas.
- Cianización mediada por cobre de los ésteres de arilboronato generados in situ.
- Optimización de las condiciones de reacción tanto para las etapas de borilación como para las de cianuración.
Principales resultados:
- Síntesis exitosa de nitriles de arilo meta-sustituidos de varias arenas y heteroarenas.
- Compatibilidad demostrada con diversos grupos funcionales, incluidos haluros, cetonas, ésteres, amidas y alcoholes protegidos.
- Conversión eficiente de un fenol protegido a un intermediario clave para la síntesis de etravirina.
- Derivación adicional de un benzonitrilo meta-sustituido a aldehídos, cetonas, amidas, ácidos carboxílicos, tetrazoles y bencilaminas.
Conclusiones:
- El método de un solo bote desarrollado proporciona una ruta eficiente y versátil para meta-sustituidos nitriles de arilo.
- Esta metodología simplifica la síntesis de compuestos aromáticos complejos con aplicaciones farmacéuticas potenciales.
- Las condiciones reportadas amplían el alcance de la funcionalización C-H y las reacciones de cianado.
![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
Videos de Conceptos Relacionados
02:47Alkynes 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.
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.
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.
01:13Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
01:20Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
03:08Hydroboration-Oxidation of Alkenes
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
01:20Electrophilic Aromatic Substitution: Nitration of Benzene
The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.