Cation-n control of regiochemistry of intramolecular Schmidt reactions en route to bridged bicyclic lactams

Org Lett. 2009 Oct 1;11(19):4386-9. doi: 10.1021/ol901771b.

Abstract

The regiochemistry of the intramolecular Schmidt reaction of 2-azidoalkylketones is controlled by placing a thioether substituent at the position adjacent to the ketone to provide access to a family of unsubstituted medium bridged twisted amides. This outcome is ascribed to the presence of stabilizing through-space interactions between the diazonium cation and the n electrons on heteroatom and does not require a locked conformation of the ketone.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Bridged Bicyclo Compounds, Heterocyclic / chemical synthesis*
  • Bridged Bicyclo Compounds, Heterocyclic / chemistry
  • Cations / chemical synthesis
  • Cations / chemistry
  • Lactams / chemical synthesis*
  • Lactams / chemistry
  • Molecular Structure
  • Stereoisomerism

Substances

  • Bridged Bicyclo Compounds, Heterocyclic
  • Cations
  • Lactams