Video Experimental Relacionado

Updated: Sep 9, 2025

Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes

Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes

Published on: September 12, 2018

Reagentes de yodo hipervalente apoyados en orto-carborano: un andamio para una mayor capacidad oxidativa

Marcus Sceney¹, Keith F White¹, Jason L Dutton¹

¹Department of Biochemistry and Chemistry, La Trobe Institute for Molecular Science, La Trobe University, Melbourne, 3086, Victoria, Australia.

Journal of the American Chemical Society

|August 28, 2025

Resumen

Los investigadores informan de nuevos compuestos de yodo hipervalente (oCb-IL2) soportados por orto-carborano. Estas nuevas especies demuestran una mayor reactividad, permitiendo la oxidación de sustratos previamente no reactivos hacia compuestos de arilo-yodo (III).

Área de la Ciencia:

Química organometálica
Química del yodo hipervalente
Química del boro

Sus antecedentes:

Los compuestos hipervalentes de yodo (III) son reactivos versátiles en la síntesis orgánica.
Los compuestos de arilo-yodo (Ar-IL2) están bien establecidos, pero tienen limitaciones en la reactividad.
Los carboranos ofrecen propiedades electrónicas y estéricas únicas para estabilizar especies reactivas.

Objetivo del estudio:

Sintetizar y caracterizar nuevas especies de yodo hipervalente (oCb-IL2) ligadas al C y soportadas por ortocarborano.
Evaluar la reactividad de estos nuevos compuestos oCb-IL2 en comparación con los compuestos Ar-IL2 tradicionales.
Explorar nuevas aplicaciones sintéticas potenciales impulsadas por una mayor reactividad.

Principales métodos:

Síntesis de complejos de yodo apoyados en orto-carborano.
Caracterización estructural utilizando cristalografía de rayos X para ejemplos clave.
Estudios computacionales (por ejemplo, DFT) para comprender las propiedades electrónicas y la reactividad.
Estudios de reactividad con varios sustratos, incluido el fluoruro de trimetilsililo.

Principales resultados:

Síntesis exitosa de la primera especie de yodo hipervalente apoyada en el ortocarburo de C, denotada como oCb-IL2 (L = F, OTf).
Verificación estructural de dos ejemplos de oCb-IF2.
Los cálculos teóricos y las observaciones sintéticas iniciales indican una mayor reactividad para oCb-IL2 en comparación con los compuestos Ar-IL2.
Demostración de una desmetilación oxidativa sin precedentes del fluoruro de trimetilsililo.

Conclusiones:

El desarrollo de compuestos oCb-IL2 representa un avance significativo en la química del yodo hipervalente.
Estos nuevos compuestos exhiben una reactividad superior, ampliando el alcance de las transformaciones oxidativas accesibles.
Los reactivos oCb-IL2 ofrecen una alternativa prometedora para la oxidación de sustratos inertes frente a los reactivos Ar-IL2 convencionales.

Más Videos Relacionados

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

Published on: September 8, 2013

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS

Published on: June 20, 2014

Videos de Conceptos Relacionados

Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene

Electrophilic 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.

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.

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...

α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction

α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction

The method to achieve α-brominated carboxylic acids using a mixture of phosphorus tribromide and bromine is known as the Hell–Volhard–Zelinski reaction. The reaction is catalyzed by phosphorus tribromide, which can be used directly or produced in situ from red phosphorus and bromine. The mechanism comprises PBr3 catalyzed conversion of acid to acid bromide and hydrogen bromide. The acid bromide enolizes to its enol form in the presence of HBr. The nucleophilic enol attacks the...

Regioselectivity of Electrophilic Additions-Peroxide Effect

Regioselectivity of Electrophilic Additions-Peroxide Effect

In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.

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...