Video Experimental Relacionado

Updated: Feb 26, 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

Permitir el acoplamiento cruzado de nucleófilos de organoboron terciario a través de la transferencia de alquilo

David N Primer¹, Gary A Molander¹

¹Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.

Journal of the American Chemical Society

|July 19, 2017

Resumen

Un nuevo método catalítico dual fotorredóxido-níquel permite la síntesis de centros de carbono cuaternarios a través del acoplamiento cruzado. Este enfoque supera las limitaciones de las estrategias existentes que utilizan reactivos de organoboron terciario y haluros de arilo.

Área de la Ciencia:

Síntesis orgánica
Catálisis
Química medicinal

Sus antecedentes:

La construcción de centros de carbono cuaternarios es crucial para la síntesis de moléculas complejas.
Los métodos de acoplamiento cruzado existentes para estos centros son limitados y a menudo requieren reactivos agresivos.

Objetivo del estudio:

Desarrollar una nueva estrategia catalítica de amplia aplicación para la formación de centros cuaternarios.
Para permitir el acoplamiento de reactivos de organoboron terciario con haluros de arilo.

Principales métodos:

Desarrollo de un sistema catalítico dual de fotorreducción y níquel.
Se utilizaron reactivos orgánicos terciarios y haluros de arilo como socios de acoplamiento.
Se realizaron estudios exhaustivos de detección y mecanicistas.

Principales resultados:

Se estableció con éxito una nueva estrategia catalítica dual.
Se ha demostrado el acoplamiento cruzado de reactivos orgánicos terciarios con haluros de arilo.
Se examinó el alcance y las limitaciones de la nueva metodología.

Conclusiones:

La catálisis dual fotorredóxido-Ni reportada ofrece una nueva herramienta valiosa para la construcción de centros cuaternarios.
Este método ofrece una alternativa a los enfoques sintéticos tradicionales, a menudo menos versátiles.

Más Videos Relacionados

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

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species

Published on: August 16, 2018

Videos de Conceptos Relacionados

Radical Reactivity: Nucleophilic Radicals

Radical Reactivity: Nucleophilic Radicals

Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...

Radical Substitution: Allylic Bromination

Radical Substitution: Allylic Bromination

In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...

Hydroboration-Oxidation of Alkenes

Hydroboration-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.

Radical Anti-Markovnikov Addition to Alkenes: Overview

Radical Anti-Markovnikov Addition to Alkenes: Overview

The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.

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.

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...