Mesoionic 1,3-oxazinium olates. rearrangement to acylketenes and 3-azabicyclo[3.1.1]heptanetriones

J Org Chem. 2005 Jul 22;70(15):5859-61. doi: 10.1021/jo050428m.

Abstract

Metastable but isolable mesoionic 1,3-oxazinium 4-olates 9d-f undergo ring opening to acylketenes 10 at or near room temperature. The ketenes undergo intramolecular criss-cross [2 + 2] cycloaddition to afford 3-azabicyclo[3.1.1]heptanetriones 12. The structure of 12d was established by X-ray crystallography.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aza Compounds / chemistry*
  • Bridged Bicyclo Compounds, Heterocyclic / chemistry*
  • Crystallography, X-Ray
  • Enzyme Inhibitors / chemical synthesis
  • Enzyme Inhibitors / pharmacology
  • Ethylenes / chemistry*
  • Heptanes / chemistry
  • Ketones / chemistry*
  • Oxazines / chemical synthesis*
  • Oxazines / pharmacology
  • Oxazoles / chemical synthesis*
  • Oxazoles / pharmacology

Substances

  • Aza Compounds
  • Bridged Bicyclo Compounds, Heterocyclic
  • Enzyme Inhibitors
  • Ethylenes
  • Heptanes
  • Ketones
  • Oxazines
  • Oxazoles
  • ketene