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The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the...
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Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
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Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
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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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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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Phosphorane-Promoted C-C Coupling during Aryne Annulations.

Paul V Kevorkian1, Dorian S Sneddon1, Casey B Ritts1

  • 1Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, USA.

Angewandte Chemie (International Ed. in English)
|February 7, 2024
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Arynes react with phosphoranes to form novel helical polycyclic aromatic compounds. This study details new synthetic routes and confirms structures using advanced computational and crystallographic methods.

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry
  • Polycyclic Aromatic Hydrocarbons

Background:

  • Arynes are highly reactive intermediates known for complex trapping reactions.
  • Their unique electrophilicity can lead to unexpected reaction pathways.
  • Formation of polycyclic aromatic compounds often involves intricate mechanisms.

Purpose of the Study:

  • To investigate the reaction of thermally generated arynes with phosphoranes.
  • To synthesize and characterize novel helical dibenzothiophenes and -selenophenes.
  • To elucidate the mechanism of this unique transformation.

Main Methods:

  • Thermal generation of arynes.
  • Reaction of arynes with phosphoranes.
  • DP4+ computational analysis for structural elucidation.
  • X-ray crystallography for structural confirmation.
  • Density Functional Theory (DFT) computations for mechanistic studies.

Main Results:

  • Successful synthesis of multiple new helical polycyclic aromatic products.
  • Confirmation of product structures using DP4+ and X-ray crystallography.
  • Demonstration of DP4+ utility in distinguishing isomeric polycyclic aromatic compounds.
  • Identification of ligand coupling (reductive elimination) as the key mechanistic step.

Conclusions:

  • Thermally generated arynes react with phosphoranes to yield helical dibenzothiophenes and -selenophenes.
  • DP4+ and X-ray crystallography are effective tools for structural determination of complex polycyclic aromatics.
  • A plausible mechanism involving reductive elimination from a hypervalent phosphorane intermediate has been proposed.