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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
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In the presence of an aqueous base and a halogen, primary amides can lose the carbonyl (as carbon dioxide) and undergo rearrangement to form primary amines. This reaction, called the Hofmann rearrangement, can produce primary amines (aryl and alkyl) in high yields without contamination by secondary and tertiary amines.
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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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At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
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The Hofmann and Curtius rearrangement reactions can be applied to synthesize primary amines from carboxylic acid derivatives such as amides and acyl azides. In the Hofmann rearrangement, a primary amide undergoes deprotonation in the presence of a base, followed by halogenation to generate an N-haloamide. A second proton abstraction produces a stabilized anionic species, which rearranges to an isocyanate intermediate via an alkyl group migration from the carbonyl carbon to the neighboring...
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The chair conformation is the most stable form of cyclohexane due to the absence of angle and torsional strain. The absence of angle strain is a result of cyclohexane’s bond angle being very close to the ideal tetrahedral bond angle of 109.5° in its chair conformer. Similarly, the torsional strain is also absent owing to the perfectly staggered arrangement of bonds.
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Single Atom Ring Contraction of Peptide Macrocycles Using Cornforth Rearrangement.

Sungjoon Huh1, George J Saunders1, Andrei K Yudin1

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Summary

Researchers repurposed the Cornforth rearrangement for single-atom ring contraction in cyclic peptides. This novel chemical synthesis method enables conformation-activity studies and installs unique building blocks.

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Conformational AnalysisCyclic PeptidesHeterocycle RearrangementMacrocyclesRing Contraction

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry
  • Medicinal Chemistry

Background:

  • Site-selective transformations of complex molecular scaffolds are crucial in chemical synthesis.
  • Cyclic peptides are important biomolecules with diverse applications.
  • Efficient methods for modifying peptide backbones are needed.

Purpose of the Study:

  • To repurpose the Cornforth rearrangement for single-atom ring contraction in cyclic peptide backbones.
  • To investigate the kinetics and influencing factors of this novel rearrangement.
  • To enable new approaches for conformation-activity relationship studies and macrocycle synthesis.

Main Methods:

  • Utilized the Cornforth rearrangement for peptide backbone modification.
  • Performed kinetic studies to analyze reaction efficiency.
  • Conducted conformational analysis of peptide substrates.
  • Explored the installation of non-traditional building blocks.

Main Results:

  • Successfully achieved single-atom ring contraction in cyclic peptides.
  • Identified electronic factors, ring size, and linker type as key determinants of reaction efficiency.
  • Demonstrated substrate-dependent reaction profiles linked to conformational differences.
  • Showcased the ability to incorporate building blocks incompatible with traditional methods.

Conclusions:

  • The repurposed Cornforth rearrangement offers a novel route for cyclic peptide modification.
  • This methodology facilitates detailed conformation-activity studies.
  • The approach expands the synthetic toolkit for creating complex macrocyclic structures.