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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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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.
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Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors01:31

Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors

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The Diels–Alder reaction is thermally reversible, meaning that the reaction reverts to the starting diene and dienophile under suitable temperatures. The forward reaction gives a cyclohexene derivative and is favored at low to medium temperatures. The reverse process, also called retro-Diels–Alder reaction, is a ring-opening process favored at high temperatures.
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Stereochemical Effects of Enolization01:12

Stereochemical Effects of Enolization

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The chiral α-carbon of the carbonyl compound is the stereocenter of the molecule. As shown in the figure below, when such a carbonyl compound undergoes racemization under an acidic or basic condition, an achiral enol is formed.
2.5K
Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

4.1K
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.
4.1K
Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

2.2K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
2.2K
Woodward–Hoffmann Selection Rules and Microscopic Reversibility01:34

Woodward–Hoffmann Selection Rules and Microscopic Reversibility

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Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
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Author Spotlight: In Silico Creation and Impact of Carbonylated Amino Acids on Protein Structure and Function
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Contra-Thermodynamic Stereochemical Editing.

Haotong Bai1, Na Zhang2, Qifeng Lin1

  • 1Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing 100084, China.

The Journal of Organic Chemistry
|November 29, 2025
PubMed
Summary
This summary is machine-generated.

Contra-thermodynamic stereochemical editing overcomes energy barriers to convert molecules into high-energy forms. Key challenges involve energy compensation and chirality enrichment, driving innovation in chemical synthesis.

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Area of Science:

  • Organic Chemistry
  • Stereochemistry
  • Chemical Synthesis

Background:

  • Thermodynamic stability often limits synthetic pathways.
  • Achieving high-energy stereochemical configurations is synthetically challenging.
  • Controlling chirality is crucial in many chemical and biological processes.

Purpose of the Study:

  • To highlight advancements in contra-thermodynamic stereochemical editing.
  • To discuss mechanisms enabling the conversion to high-energy stereochemical configurations.
  • To review strategies for overcoming thermodynamic barriers in stereochemical transformations.

Main Methods:

  • Focus on energy compensation mechanisms.
  • Integration of various energy sources.
  • Utilizing chiral sources for enrichment.
  • Analysis of autoamplification, deracemization, and epimerization reactions.

Main Results:

  • Demonstration of strategies to overcome thermodynamic stability.
  • Methods for achieving high-energy stereochemical configurations.
  • Successful examples of chirality enrichment in reactions.
  • Insights into the mechanisms driving these transformations.

Conclusions:

  • Contra-thermodynamic stereochemical editing is a powerful synthetic strategy.
  • Energy compensation and chirality enrichment are key design principles.
  • This approach enables access to valuable high-energy molecular architectures.