Solvent-catalyzed ring-chain-ring tautomerization in axially chiral compounds

Asli Yildirim, Fethiye Aylin Sungur Konuklar, Saron Catak*, Veronique Van Speybroeck, Michel Waroquier, Ilknur Dogan, Viktorya Aviyente

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)


The mechanism of ring-chain-ring tautomerization and the prominent effect of the solvent environment have been computationally investigated in an effort to explain the enantiomeric interconversion observed in 2-oxazolidinone derivatives, heterocyclic analogues of biphenyl atropisomers, which were isolated as single stable enantiomers and have the potential to be used as axially chiral catalysts. This study has shed light on the identity of the intermediate species involved in the ring-chain-ring tautomerization process as well as the catalytic effect of polar protic solvents. These mechanistic details will prove very useful in predicting and understanding ring-chain tautomeric equilibria in similar heterocyclic systems and will further enable experimentalists to devise appropriate experimental conditions in which axially chiral catalysts remain stable as single enantiomers. Tautomerism mechanisms: 2-Oxazolidinone derivatives have the potential to be used as axially chiral catalysts. However, they thermally interconvert by a ring-chain-ring tautomerization mechanism (see scheme). DFT calculations provide a thorough understanding of this mechanism as well as the effect of solvent assistance, which is crucial for facilitating proton transfer.

Original languageEnglish
Pages (from-to)12725-12732
Number of pages8
JournalChemistry - A European Journal
Issue number40
Publication statusPublished - 1 Oct 2012


  • biaryls
  • chirality
  • density functional calculations
  • microsolvation
  • tautomerization


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