One-pot synthesis of γ -spiroiminolactones and γ -dispiroiminolactones using N,N'-disubstituted parabanic acid and thioparabanic acid derivatives

Mol Divers. 2017 Feb;21(1):69-79. doi: 10.1007/s11030-016-9698-3. Epub 2016 Sep 20.

Abstract

A direct entry and simple process for the synthesis of [Formula: see text]-spiroiminolactones present in a large number of natural products has been developed. In the first step, the synthesis of parabanic acid derivatives was commenced from the reaction of [Formula: see text]-disubstituted urea and thiourea with oxalyl chloride, then a three-component reaction was carried out with isocyanides, acetylenic esters, and [Formula: see text]-disubstituted parabanic acid derivatives. The method allows the construction of a variety of [Formula: see text]-spiroiminolactone structures in good to high yields starting from readily available precursors. It was found that in the case of [Formula: see text]-diphenyl thioparabanic acid, additional products of [Formula: see text]-dispiroiminolactones have been formed due to the higher electrophilicity of [Formula: see text]-dicarbonyl groups. The structures were fully established using spectroscopic analysis NMR, IR, and Mass spectrometry. The crystal structure of [Formula: see text]-dispiroiminolactone was confirmed from single-crystal X-ray diffraction study.

Keywords: -Dispiroiminolactones; -spiroiminolactones; Dialkyl acetylenedicarboxylates; Isocyanide; Parabanic acid derivatives; Zwitterionic intermediate.

MeSH terms

  • Chemistry Techniques, Synthetic
  • Hydantoins / chemistry*
  • Lactones / chemical synthesis*
  • Lactones / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Spiro Compounds / chemistry*
  • Stereoisomerism

Substances

  • Hydantoins
  • Lactones
  • Spiro Compounds
  • parabanic acid