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Autocatalysis in Eschenmoser Coupling Reactions.

Quentin Duez1, Lukáš Marek2, Jiří Váňa2

  • 1Institute for Molecules and Materials, Faculty of Science, Radboud University, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|December 13, 2023
PubMed
Summary

The Eschenmoser coupling reaction (ECR) mechanism was elucidated without external agents. Polysulfide species (Sⁿ) were identified as key intermediates, revealing the reaction

Keywords:
AutocatalysisDensity functional theory calculationsFlow chemistryIon mobilityMass spectrometryReaction mechanismsVibrational spectroscopy

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Area of Science:

  • Organic Chemistry
  • Reaction Mechanisms

Background:

  • The Eschenmoser coupling reaction (ECR) is a vital synthetic method.
  • Its mechanism, particularly the fate of thiirane intermediates, remains incompletely understood.
  • Previous studies relied on external thiophiles, complicating mechanistic interpretation.

Purpose of the Study:

  • To investigate the ECR mechanism in the absence of external thiophiles or bases.
  • To identify the elusive intermediates responsible for product formation.
  • To gain a comprehensive understanding of the ECR reaction pathway.

Main Methods:

  • Electrospray ionization-mass spectrometry (ESI-MS) for intermediate detection.
  • Ion mobility spectrometry and ion spectroscopy for structural characterization.
  • Flow chemistry coupled with mass spectrometry for real-time reaction monitoring.

Main Results:

  • Detection and characterization of polysulfide species (Sⁿ, n=2-16) as key intermediates.
  • Observation of ECR proceeding without added thiophiles or bases.
  • Identification of an autocatalytic pathway in the Eschenmoser coupling reaction.

Conclusions:

  • Polysulfide species are crucial for ECR product formation.
  • The ECR reaction exhibits autocatalysis, influencing its efficiency.
  • This study provides novel mechanistic insights into the Eschenmoser coupling reaction.