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Related Concept Videos

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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Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

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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.
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[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

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The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
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Thermal Electrocyclic Reactions: Stereochemistry01:17

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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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Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

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Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
2.7K
Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

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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.
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Unraveling Entropic Rate Acceleration Induced by Solvent Dynamics in Membrane Enzymes
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Reversible Macrocycle-to-Macrocycle Interconversion Driven by Solvent Selection.

Fei Wang1, Xiangling Shi1, Yi Zhang1

  • 1State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China.

Journal of the American Chemical Society
|May 12, 2023
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Summary
This summary is machine-generated.

Researchers developed a new one-pot synthesis for self-assembled macrocycles. Solvent choice controls the formation of different sized macrocyclic products, enabling reversible interconversions between [1 + 1] and [2 + 2] structures.

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Area of Science:

  • Supramolecular Chemistry
  • Organic Synthesis
  • Materials Science

Background:

  • Macrocycle-to-macrocycle interconversions offer diverse structural possibilities.
  • Achieving controlled, reversible interconversions between macrocycles of varying sizes presents a significant challenge.

Purpose of the Study:

  • To develop a facile one-pot synthesis for self-assembled macrocycles.
  • To investigate the control of macrocycle size and interconversion through solvent manipulation.

Main Methods:

  • Condensation reactions between α,α'-linked oligopyrrolic dialdehydes and alkyl diamines.
  • Utilizing various solvents (methanol, ethanol, chloroform, DMSO, DMF, MeCN) to influence product distribution.
  • Characterization of macrocyclic products ([1 + 1] and [2 + 2] assemblies).

Main Results:

  • A pyridine-bridged oligopyrrolic dialdehyde (3) and alkyl diamines readily form [2 + 2] macrocycles, independent of solvent.
  • Condensation of 3 with 2,2'-oxybis(ethylamine) (14) yields either [1 + 1] or [2 + 2] macrocycles based on solvent choice.
  • Specific solvents (methanol, ethanol, chloroform) favor [1 + 1] products, while others (DMSO, DMF, MeCN) favor [2 + 2] products, often as precipitates.
  • Reversible interconversion between [1 + 1] and [2 + 2] macrocycles is achievable by altering the solvent, driven by thermodynamic and solubility factors.

Conclusions:

  • A versatile one-pot method for synthesizing self-assembled macrocycles has been established.
  • Solvent-controlled reversible macrocycle interconversions are demonstrated, offering a new strategy for structural diversity.
  • The findings highlight the importance of thermodynamic and solubility parameters in directing self-assembly processes.