Video Experimental Relacionado

Updated: Sep 28, 2025

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

Activación del radical borilo del enlace bencílico C-OH: acoplamiento electrófilo cruzado de alcoholes libres y CO2 a

Wen-Duo Li¹, Yang Wu¹, Shi-Jun Li²

¹State Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Lanzhou Institute of Chemical Physics (LICP), University of Chinese Academy of Sciences, Chinese Academy of Sciences, Lanzhou 730000, China.

Journal of the American Chemical Society

|April 4, 2022

Resumen

Los investigadores desarrollaron un nuevo método para la escisión directa de enlaces C-OH con alcohol utilizando radicales de boro bajo luz visible. Esto permite la síntesis de ácidos carboxílicos a través del acoplamiento de dióxido de carbono, transformando varios alcoholes de manera eficiente.

Área de la Ciencia:

Química orgánica
Catalización por fotorreducción
Metodología sintética

Sus antecedentes:

La funcionalización directa del enlace C ((sp3) -OH en los alcoholes sigue siendo un desafío importante en la síntesis orgánica.
Los métodos existentes a menudo requieren condiciones duras o pre-funcionalización del alcohol.
El desarrollo de estrategias suaves y eficientes para la activación del alcohol es crucial para la síntesis sostenible.

Objetivo del estudio:

Desarrollar una nueva estrategia para la escisión directa del enlace C ((sp3) -OH en alcoholes libres.
Para lograr la síntesis de ácidos carboxílicos mediante el acoplamiento electrofilo cruzado de alcoholes con dióxido de carbono.
Explorar el alcance y el mecanismo de esta nueva transformación.

Principales métodos:

Catálisis de fotorreducción por luz visible utilizando un radical neutro de difenil borilo generado a partir del tetrafenilborato de sodio.
Activación de los alcoholes libres (alcoholes bencílicos primarios, secundarios y terciarios)
Acoplamiento electrofilo cruzado con dióxido de carbono (CO2).

Principales resultados:

Clivado directo exitoso del enlace C ((sp3) -OH en una variedad de alcoholes bencílicos.
Síntesis eficiente de ácidos carboxílicos mediante el acoplamiento con CO2.
Demostración de la aplicabilidad del método a los alcoholes primarios, secundarios y terciarios.

Conclusiones:

Se ha establecido una nueva y leve estrategia de fotorreducción para la escisión directa del enlace C ((sp3) -OH.
El método desarrollado proporciona una ruta fácil a los ácidos carboxílicos de los alcoholes y el CO2 fácilmente disponibles.
Las investigaciones mecánicas sugieren una vía que involucra la activación del radical borilo, la homólisis del enlace C-OH, la reducción del radical alquilo y la posterior carboxilación.

Más Videos Relacionados

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Published on: November 9, 2019

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Published on: April 4, 2014

Videos de Conceptos Relacionados

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.

Preparation of Alcohols via Addition Reactions

Preparation of Alcohols via Addition Reactions

Overview
The acid-catalyzed addition of water to the double bond of alkenes is a large-scale industrial method used to synthesize low-molecular-weight alcohols. An acidic atmosphere is required to allow the hydrogen in the water molecule to act as an electrophile and attack the double bond in an alkene. The addition of a proton to the double bond creates a carbocation intermediate. The proton preferentially bonds to the less substituted end of the double bond to create a more stable carbocation...

Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation

Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation

Baeyer–Villiger oxidation converts aldehydes to carboxylic acids and ketones to esters. The reaction uses peroxy acids or peracids and is often catalyzed by acid. The reaction is named after its pioneers, Adolf von Baeyer and Victor Villiger. The reaction is achieved by a wide range of peracids such as m-chloroperoxybenzoic acid (mCPBA), perbenzoic acid (C6H5COOOH), peracetic acid (CH3COOOH), hydrogen peroxide (H2O2), and tert-butyl hydroperoxide (t-BuOOH).
The carbonyl center 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...

Radical Oxidation of Allylic and Benzylic Alcohols

Radical Oxidation of Allylic and Benzylic Alcohols

Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...

Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview

Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview

Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of aldehydes or ketones in the presence of hydrocarbon solvent to yield vicinal diols.