Intramolecular nucleophilic carbonyl trapping of alpha-ketenyl radicals by an amino group

Chem Commun (Camb). 2004 Nov 7:(21):2482-3. doi: 10.1039/b408746a. Epub 2004 Sep 14.

Abstract

Free-radical carbonylation of omega-alkynylamines with tributyltin hydride gives a mixture of alpha-methylene lactams and alpha-stannylmethylene lactams. Nucleophilic addition of an internal amino group to the carbonyl group of alpha-ketenyl radicals is proposed as the cyclization step. The subsequent unusual 1,4-H shift from the resulting 1-hydroxyallyl radical, followed by elimination of the beta-tributyltin radical leads to the formation of alpha-methylene lactams.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amines / chemical synthesis*
  • Cyclization
  • Ethylenes / chemistry*
  • Free Radicals / chemistry
  • Ketones / chemistry*
  • Molecular Structure
  • Trialkyltin Compounds / chemistry

Substances

  • Amines
  • Ethylenes
  • Free Radicals
  • Ketones
  • Trialkyltin Compounds
  • tributyltin
  • ketene