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Radical Autoxidation01:20

Radical Autoxidation

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The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
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Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide02:44

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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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Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids02:04

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

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Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
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Regioselectivity and Stereochemistry of Hydroboration02:36

Regioselectivity and Stereochemistry of Hydroboration

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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.
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Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule02:17

Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule

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If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
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Regioselectivity of Electrophilic Additions-Peroxide Effect02:35

Regioselectivity of Electrophilic Additions-Peroxide Effect

10.3K
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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Stereoselectivity in Atmospheric Autoxidation.

Kristian H Møller1, Eric Praske2, Lu Xu3

  • 1Department of Chemistry , University of Copenhagen , DK-2100 Copenhagen Ø , Denmark.

The Journal of Physical Chemistry Letters
|September 24, 2019
PubMed
Summary
This summary is machine-generated.

Diastereomers of hydroxy peroxy radicals from crotonaldehyde exhibit significant differences in their H-shift chemistry. This stereoselective gas-phase reaction enhances specific stereoisomers, impacting atmospheric chemistry.

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Area of Science:

  • Atmospheric Chemistry
  • Organic Chemistry
  • Chemical Kinetics

Background:

  • Chirality is ubiquitous in nature, influencing biological and chemical processes.
  • Understanding the atmospheric fate of volatile organic compounds (VOCs) is crucial for air quality.
  • Peroxy radicals are key intermediates in the oxidation of VOCs in the atmosphere.

Purpose of the Study:

  • To investigate the gas-phase unimolecular chemistry of hydroxy peroxy radicals derived from crotonaldehyde.
  • To determine the rate coefficients for the aldehydic hydrogen shift (H-shift) reaction.
  • To assess the stereospecificity of these reactions and their atmospheric implications.

Main Methods:

  • Experimental measurements using stereoisomer-specific gas-chromatography chemical ionization mass spectroscopy (GC-CIMS).
  • Theoretical calculations employing multiconformer transition state theory (MC-TST).
  • Synthesis and characterization of diastereomers of hydroxy peroxy radicals from crotonaldehyde.

Main Results:

  • Diastereomers of hydroxy peroxy radicals from crotonaldehyde show an order of magnitude difference in H-shift rate coefficients.
  • The observed stereospecificity in H-shift chemistry is significant.
  • Calculated H-shift rate coefficients using MC-TST show excellent agreement with experimental GC-CIMS data.

Conclusions:

  • Stereoselective gas-phase reactions can enhance specific stereoisomers in the atmosphere.
  • This stereoisomer-specific chemistry has widespread implications due to the prevalence of chirality.
  • The study validates MC-TST as a reliable method for predicting H-shift kinetics in complex systems.