Video Experimental Relacionado

Updated: Mar 6, 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

Funcionalización C-O de los α-oxiboronatos: una gem-diborilación y gem-siliborilación desoxigenativas de los

Lu Wang¹, Tao Zhang^1,2, Wei Sun¹

¹State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences , Lanzhou 730000, P. R. China.

Journal of the American Chemical Society

|March 18, 2017

Resumen

Este estudio introduce una nueva diborilación y sililborilación de gemas desoxigenativas de aldehídos y cetonas. El método utiliza la funcionalización del enlace C-O promovido por la base de los α-oxiboronatos para una síntesis eficiente.

Área de la Ciencia:

Química orgánica
Catálisis
Metodología sintética

Sus antecedentes:

Los aldehídos y las cetonas son compuestos carbonílicos versátiles.
La funcionalización desoxigenativa eficiente de los carbonilos sigue siendo un desafío sintético.
Los compuestos que contienen boro son valiosos intermedios sintéticos.

Objetivo del estudio:

Desarrollar una nueva diborilación desoxigenativa de gemas de aldehídos y cetonas.
Para obtener gem-sililborilación de aldehídos y cetonas.
Para aclarar el mecanismo de reacción.

Principales métodos:

La diborilación desoxigenativa catalizada por el cobre mediante el uso de bis ((pinacolato) diboro (B2pin2).
La siliborilación gradual de gemas implica una borilación inicial seguida de una silidación.
Estudios experimentales y teóricos para investigar la vía de reacción.

Principales resultados:

El éxito de la desoxigenación gem-diborilación de varios aldehídos y cetonas.
Eficiencia de la sililborilación de gemas obtenida mediante un proceso escalonado.
El mecanismo implica la migración intramolecular de borilo y el reordenamiento de 1,2-metalato con inversión en el centro de carbono.

Conclusiones:

Se establece una nueva vía sintética para los compuestos de carbonilo gem-diborilados y gem-siliborilados.
La metodología desarrollada ofrece una herramienta valiosa para la síntesis orgánica.
Comprender el mecanismo proporciona información sobre las estrategias de funcionalización de los bonos C-O.

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

Regioselective O-Glycosylation of Nucleosides via the Temporary 2',3'-Diol Protection by a Boronic Ester for the Synthesis of Disaccharide Nucleosides

Regioselective O-Glycosylation of Nucleosides via the Temporary 2',3'-Diol Protection by a Boronic Ester for the Synthesis of Disaccharide Nucleosides

Published on: July 26, 2018

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.

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.

Aldehydes and Ketones with Water: Hydrate Formation

Aldehydes and Ketones with Water: Hydrate Formation

An oxygen-based nucleophile, like water, can undergo addition reactions with aldehydes and ketones. The reaction leads to the formation of hydrates, also referred to as 1,1-diols or geminal diols.
The formation of hydrates is a reversible reaction. Hydrate formation is influenced by steric and electronic factors accompanying the alkyl substituents on the carbonyl group: The rate of hydrate formation increases with a decrease in the number of alkyl groups attached to the carbonyl carbon. Hence,...

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.

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.

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 activated by...