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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

2.1K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.1K
Five-Membered Heterocyclic Aromatic Compounds: Overview01:13

Five-Membered Heterocyclic Aromatic Compounds: Overview

4.1K
Heterocyclic aromatic compounds are cyclic compounds that are aromatic and have one or more heteroatoms—atoms other than carbon, in the ring. Depending upon the number of atoms present in the ring, they can be either five or six-membered. Examples of five-membered heterocyclic aromatic compounds include pyrrole, furan, thiophene, and imidazole. Pyrrole consists of one nitrogen atom having one lone pair of electrons. Furan and thiophene have one oxygen and one sulfur heteroatom,...
4.1K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction01:16

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

10.4K
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
10.4K
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

2.4K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.4K
Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

3.6K
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
3.6K
Structure of Conjugated Dienes01:16

Structure of Conjugated Dienes

5.3K
Introduction
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...
5.3K

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Updated: Aug 11, 2025

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
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A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

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Direct Heteroarylation Guidelines for Well-Defined Thiophene-Based Conjugated Molecules.

Mona Hamidzad Sangachin1, Samuel Brassard1, Mario Leclerc1

  • 1Université Laval, Département de Chimie, Québec City G1V 0A6, Canada.

The Journal of Organic Chemistry
|February 9, 2023
PubMed
Summary
This summary is machine-generated.

Direct (hetero)arylation polymerization (DHAP) offers a cost-effective way to create conjugated polymers. Researchers found that halogenating the electron-withdrawing component improves coupling selectivity in this process.

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Area of Science:

  • Organic Chemistry
  • Polymer Science
  • Materials Science

Background:

  • Direct (hetero)arylation polymerization (DHAP) is a promising technique for synthesizing conjugated polymers.
  • Achieving high coupling selectivity remains a challenge in DHAP.

Purpose of the Study:

  • To investigate and optimize conditions for C-C couplings in DHAP.
  • To improve selectivity by studying small molecule models involving electron-donating and electron-withdrawing moieties.

Main Methods:

  • Studied direct (hetero)arylation reactions on small molecule models.
  • Utilized 2-methylthiophene (electron-donating) and 2-thiophenecarbonitrile (electron-withdrawing) as model compounds.
  • Varied halogenation positions on the coupling partners.

Main Results:

  • Identified optimal conditions for C-C bond formation in DHAP.
  • Demonstrated that halogenating the electron-withdrawing moiety (2-thiophenecarbonitrile) significantly enhances coupling selectivity.
  • Established a clear relationship between moiety electronics and reaction outcome.

Conclusions:

  • Optimized DHAP conditions by strategically halogenating the electron-withdrawing component.
  • This strategy provides a pathway for more efficient and selective synthesis of conjugated polymers.
  • The findings contribute to the development of cost-effective and environmentally benign polymer preparation methods.