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Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

2.6K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
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SN2 Reaction: Transition State02:26

SN2 Reaction: Transition State

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An SN2 reaction of an alkyl halide is a single-step process in which bond formation between the nucleophile and the substrate and bond breaking between the substrate and the halide occurs simultaneously through a transition state without forming an intermediate.
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
12.3K
Drugs that Stabilize Microtubules01:15

Drugs that Stabilize Microtubules

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Microtubules are dynamic structures that undergo cycles of catastrophe and rescue. The microtubules play a central role in cell division by forming the spindle apparatus for segregating the chromosomes. This makes them ideal targets for regulating dividing cells in tumors and malignant cancer cells. Microtubule stabilizing drugs help stabilize the microtubule formation and promote its polymerization. Paclitaxel was the first microtubule stabilizing agent used as anticancer drug in chemotherapy...
2.8K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule02:17

Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule

18.0K
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...
18.0K
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.9K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.9K
Radical Formation: Addition00:47

Radical Formation: Addition

2.3K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
2.3K

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Updated: Feb 28, 2026

Solid-phase Synthesis of [4.4] Spirocyclic Oximes
05:15

Solid-phase Synthesis of [4.4] Spirocyclic Oximes

Published on: February 6, 2019

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[2]Rotaxane Formation by Transition State Stabilization.

Guillaume De Bo1, Guillaume Dolphijn1, Charlie T McTernan1

  • 1School of Chemistry, University of Manchester , Oxford Road, Manchester, M13 9PL, United Kingdom.

Journal of the American Chemical Society
|June 17, 2017
PubMed
Summary

Researchers synthesized [2]rotaxanes by stabilizing the transition state during amine addition to cyclic sulfates. This novel approach utilizes a bifunctional macrocycle to control the reaction pathway, enabling efficient molecular assembly.

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Area of Science:

  • Supramolecular Chemistry
  • Organic Synthesis

Background:

  • Rotaxanes are mechanically interlocked molecular architectures with potential applications in molecular machines and materials science.
  • The synthesis of rotaxanes often relies on template-directed methods to control the assembly process.
  • Stabilizing transition states is a key strategy for enhancing reaction rates and selectivity in organic synthesis.

Purpose of the Study:

  • To report a novel strategy for the synthesis of [2]rotaxanes.
  • To demonstrate the use of a bifunctional macrocycle in stabilizing the transition state of an axle-forming reaction.
  • To investigate the role of hydrogen bonding in directing the self-assembly of rotaxane structures.

Main Methods:

  • Synthesis of a bifunctional macrocycle containing both hydrogen bond donors and acceptors.
  • Reaction of the macrocycle with a cyclic sulfate and a primary amine.
  • Characterization of the resulting [2]rotaxane product using techniques such as NMR spectroscopy and mass spectrometry.

Main Results:

  • Successful synthesis of [2]rotaxanes was achieved.
  • The bifunctional macrocycle effectively stabilized the charged transition state during the addition of the primary amine to the cyclic sulfate.
  • The hydrogen bonding interactions within the macrocycle were crucial for directing the rotaxane formation.

Conclusions:

  • The stabilization of the axle-forming transition state by a bifunctional macrocycle provides an efficient route to [2]rotaxanes.
  • This approach offers a new method for controlling molecular assembly and designing complex supramolecular structures.
  • The findings highlight the potential of using non-covalent interactions to drive and control complex chemical transformations.