Imine ⇌ Enamine Tautomerism

Koop Lammertsma, Bharatam V. Prasad

Research output: Contribution to journalArticlepeer-review

119 Citations (Scopus)


Acetaldimine ⇌ vinylamine tautomerism and their conformational preferences are studied using MP2-(full)/6-31G∗ geometries and Gaussian-2 energies. Geometrical parameters, harmonic vibrational frequencies, relative stabilities, conformational stabilities, the amine inversion barrier, ionization energies, atomization energies, and equilibrium constants are compared with experimental gas-phase data when available. Their less than satisfactory agreement results mainly from a lack of definitive experimental data. The imine ⇌ enamine tautomerism is also compared with the keto ⇌ enol and nitro ⇌ aci-nitro tautomeric processes. Solvent effects are estimated by Onsager's reaction field model (SCRF) at HF/6-31G∗ for structural parameters and vibrational frequencies, both of which are minimal, and at QCISD for energies. The anti-acetaldimine tautomer is energetically favored over vinylamine by 3.9 kcal/mol at G2 and by 4.3 kcal/mol after extrapolation of the acetonitrile solvent effect. The theoretical (gas-phase) proton affinity of the enamine anion amounts to 377 kcal/mol, and the atomization energy of acetaldimine is 697 kcal/mol. The anti conformation of acetaldimine is energetically preferred over the syn form by <1 kcal/mol, which becomes even less after inclusion of solvent effects. Similarly, the energetic preference of the syn conformer over the anti form of the enamine anion becomes negligible after inclusion of solvent effects. The effect of charges in Coulombic versus resonance delocalization in the allylic enamine anion is discussed in detail.

Original languageEnglish
Pages (from-to)642-650
Number of pages9
JournalJournal of the American Chemical Society
Issue number2
Publication statusPublished - 1 Jan 1994
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


Dive into the research topics of 'Imine ⇌ Enamine Tautomerism'. Together they form a unique fingerprint.

Cite this