(2+1)-Cycloaddition Reactions Give Further Evidence of the Nitrenium-like Character of 1-Aza-2-azoniaallene Salts

J Org Chem. 2017 Apr 7;82(7):4001-4005. doi: 10.1021/acs.joc.7b00407. Epub 2017 Mar 27.

Abstract

Cationic 1-aza-2-azoniaallene salts react with structurally constrained alkenes in intramolecular reactions by C-H insertion at the allylic position, or by (2+1)-cycloaddition with the alkene followed by ring opening. The latter reaction gives further evidence of the nitrenium-like character of 1-aza-2-azoniaallene salts. DFT calculations show that alkene addition is intrinsically more favorable, but that predistortion can lead to C-H insertion.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Alkenes / chemistry*
  • Azo Compounds / chemistry*
  • Carbon-13 Magnetic Resonance Spectroscopy
  • Cycloaddition Reaction*
  • Molecular Structure
  • Proton Magnetic Resonance Spectroscopy
  • Salts / chemistry
  • Spectrometry, Mass, Electrospray Ionization

Substances

  • Alkenes
  • Azo Compounds
  • Salts