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Catalysis02:50

Catalysis

26.6K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
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Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate02:21

Oxidation of Alkenes: Syn Dihydroxylation with Potassium Permanganate

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Alkenes can be dihydroxylated using potassium permanganate.  The method encompasses the reaction of an alkene with a cold, dilute solution of potassium permanganate under basic conditions to form a cis-diol along with a brown precipitate of manganese dioxide.
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Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide02:44

Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

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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.
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Regioselectivity of Electrophilic Additions-Peroxide Effect02:35

Regioselectivity of Electrophilic Additions-Peroxide Effect

8.4K
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.
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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
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Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation02:47

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

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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.
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Related Experiment Video

Updated: Jun 5, 2025

Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
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Heterogeneous Catalytic Oxidations with In Situ-Generated Hypervalent Iodine-Based Porous Organic Polymers.

Parag Tamuly1, Keshaba Nanda Parida2,3, Stéphane Quideau4,5

  • 1Department of Chemistry, Indian Institute of Technology, Kanpur, 208016, India.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|December 15, 2024
PubMed
Summary
This summary is machine-generated.

Novel porous organic polymers (POPs) act as stable heterogeneous precatalysts. These materials enable in situ generation of hypervalent iodine(V) species for efficient and recyclable oxidative transformations.

Keywords:
Heterogeneous catalysisHypervalent iodine compoundsOrganocatalysisOxidationPorous organic polymers

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Area of Science:

  • Materials Science
  • Organic Chemistry
  • Catalysis

Background:

  • Porous organic polymers (POPs) offer excellent stability for heterogeneous organocatalysis.
  • Hypervalent iodine compounds are effective oxidants but can be hazardous.

Purpose of the Study:

  • To develop novel POP-based precatalysts for the in situ generation of hypervalent iodine(V) species.
  • To demonstrate their utility in diverse heterogeneous oxidative transformations.
  • To address the safety concerns associated with traditional hypervalent iodine reagents.

Main Methods:

  • Synthesis of o-iodobenzoic acid (IA)-functionalized POPs (IA-POPs) via Friedel-Crafts alkylation.
  • In situ oxidation of IA-POPs using Oxone® to generate hypervalent iodine(V) species (λ⁵-iodanes).
  • Application of the heterogeneous precatalyst for various oxidation reactions.

Main Results:

  • Successfully synthesized three IA-POP precatalysts: p-OMeIA-POP, DiMeIA-POP, and m-OMeIA-POP.
  • Demonstrated efficient oxidation of alcohols to carbonyls, cleavage of olefins and diols, and oxidation of diols to lactones using m-OMeIA-POP.
  • Showcased the recyclability of the IA-precatalyst without loss of activity.
  • Confirmed in situ generation of λ⁵-iodanes in catalytic amounts, mitigating explosion risks.

Conclusions:

  • Developed the first IA-bearing POP precatalysts for in situ generation of hypervalent iodine(V) species.
  • Established a safe and recyclable heterogeneous catalytic system for various oxidative transformations.
  • Highlighted the potential of POPs as robust platforms for developing advanced catalytic materials.