A mechanistic study of the participation of azomethine ylides and carbonyl ylides in [3+2] cycloaddition reactions

Luis R. Domingo, Maria J. Aurell, Patricia Pérez

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)

Abstract

The participation of azomethine ylides (AYs) and carbonyl ylides (CYs) in [3+2] cycloaddition (32CA) reactions has been analysed at the DFT B3LYP/6-31G(d) level. The asymmetric substitution breaks the pseudodiradical character of the simplest three-atom-components (TACs), modifying their electrophilic and nucleophilic behaviours. These TACs react quickly towards electrophilic nitroethylene. However, while the reaction with AY takes place via a zw-type mechanism, the reaction with CY appears to take place via a pr-type mechanism. A different behaviour is found in the reactivity towards the nucleophilic methyl vinyl ether. While AY presents a high activation energy, CY presents a high reactivity via a pr-type mechanism. These reactions are completely regioselective, displaying exo stereoselectivity. The present study makes it possible to establish that the substitution provokes a different reactivity pattern in these TACs; while in CYs does not substantially modify their pr-type reactivity, AYs only participate in zw-type 32CA reactions towards electrophilic ethylenes.

Original languageEnglish
Pages (from-to)1050-1057
Number of pages8
JournalTetrahedron
Volume71
Issue number7
DOIs
Publication statusPublished - 18 Feb 2015

Keywords

  • Azomethine ylides
  • Carbonyl ylides
  • DFT calculations
  • Molecular mechanisms
  • [3+2] Cycloaddition reactions

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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