Zooming in on the hydrated imidazoline ring expansion: Factors influencing the rate of N → N′ aroyl migration in N-aroyl-N-(hetero)aryl ethylenediamines

Kseniya Lavit, Elena Reutskaya, Sergey Grintsevich, Alexander Sapegin, Mikhail Krasavin

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

The influence of electronic factors on the rates of N → N′ aroyl migration in N-aroyl-N-(hetero)aryl ethylenediamines has been examined. Electron-withdrawing substituents on the aroyl group were found to weakly accelerate the reaction (in linear correlation with the Hammett σp constants). Much stronger influence came from the nitrogen-bound aromatic group which gave a strong linear correlation with the Hammett σp constants. For electron-deficient heteroaromatics and nitroaromatics, the migration was nearly instantaneous in basic medium. These findings will significantly impact the planning of mechanistically related transformations of N-(2-aminoethyl) lactams through the hydrated imidazoline ring expansion (HIRE) process.

Original languageEnglish
Article number152423
Number of pages4
JournalTetrahedron Letters
Volume61
Issue number42
DOIs
StatePublished - 15 Oct 2020

Scopus subject areas

  • Drug Discovery
  • Biochemistry
  • Organic Chemistry

Keywords

  • Addition-elimination
  • Base-promoted reaction
  • Hammett σ and σ constants
  • Hydrated imidazoline ring expansion
  • N → N′ acyl migration
  • Hammett σp and σp− constants
  • 1-ARYL-2-PHENYL-2-IMIDAZOLINES
  • HYDROLYSIS
  • Hammett sigma(p) and sigma(-)(p) constants
  • BASICITY-RATE
  • N -> N' acyl migration

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