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Isomerism in Alkenes02:01

Isomerism in Alkenes

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Alkenes like 1-butene and 2-butene exhibit constitutional isomerism, as they differ in the position of the double bond. Further, 2-butene exhibits stereoisomerism and exists as two distinct compounds differing in spatial arrangement.
An isomer is called cis-2-butene when the methyl groups are on the same side of the double bond, and the other stereoisomer, in which methyl groups are on the opposite side of the double bond, is called trans-2-butene. The cis and trans stereoisomers are not...
12.0K
Conformations of Cycloalkanes02:29

Conformations of Cycloalkanes

11.9K
Adolf von Baeyer attempted to explain the instabilities of small and large cycloalkane rings using the concept of angle strain — the strain caused by the deviation of bond angles from the ideal 109.5° tetrahedral value for sp3  hybridized carbons. However, while cyclopropane and cyclobutane are strained, as expected from their highly compressed bond angles, cyclopentane is more strained than predicted, and cyclohexane is virtually strain-free. Hence, Baeyer’s theory that...
11.9K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule02:17

Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule

14.3K
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...
14.3K
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement01:24

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

2.2K
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
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Halogenation of Alkenes02:46

Halogenation of Alkenes

15.8K
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
15.8K
Disubstituted Cyclohexanes: cis-trans Isomerism02:37

Disubstituted Cyclohexanes: cis-trans Isomerism

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Depending upon the different spatial orientation of the substituents, the disubstituted cycloalkanes exhibit two types of stereoisomers. The cis isomers have the substituents on the same side of the ring, whereas the trans isomers have the substituents on the opposite sides. These stereoisomers exhibit different physical properties and cannot be interconverted without breaking the carbon-carbon bonds.
In cyclohexane, the substituents can occupy different positions generating distinct isomers....
12.0K

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Updated: Jul 17, 2025

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers
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Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers

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Isomerización posicional del alqueno inductora de deformación

Vignesh Palani1, Alison E Wendlandt1

  • 1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.

Journal of the American Chemical Society
|August 30, 2023
PubMed
Resumen

Los investigadores desarrollaron un nuevo método para crear moléculas de ciclobuteno tensadas a partir de precursores de ciclobutilideno. Esta isomerización de alqueno inductora de tensión utiliza fotocatálisis y un co-catalizador, ofreciendo una ruta suave a bloques de construcción sintéticos valiosos.

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Área de la Ciencia:

  • Química orgánica
  • Fotocatálisis
  • Química medicinal

Sus antecedentes:

  • Los sistemas de anillos pequeños y tensos son cruciales en la química medicinal y la síntesis orgánica.
  • La inestabilidad de las moléculas orgánicas tensas dificulta su preparación.

Objetivo del estudio:

  • Desarrollar un método suave y selectivo para acceder a los bloques de construcción de ciclobuteno.
  • Para utilizar una reacción de isomerización de alqueno posicional inductora de deformación.

Principales métodos:

  • Utilizando un fotocatalizador de polianiones en estado de decaturación y un cocatalizador de cobalxima.
  • Utilizando precursores de ciclobutilideno fácilmente obtenidos.
  • Investigar las vías mecanicistas a través de estudios detallados.

Principales resultados:

  • Se ha logrado una síntesis leve y selectiva de los componentes del ciclobuteno.
  • Demostró la versatilidad de los productos de ciclobuteno a través de transformaciones de liberación de tensión.
  • Se identificó una base estérica para la formación de productos selectivos de cepas.

Conclusiones:

  • La isomerización inductora de tensión reportada proporciona un acceso eficiente a los valiosos intermedios del ciclobuteno.
  • El sistema sinérgico de fotocatalizador y cocatalizador permite el almacenamiento de energía a través de la tensión del anillo.
  • La metodología ofrece una plataforma versátil para las aplicaciones de síntesis orgánica y química medicinal.