Cobalt-mediated [2+2+2] cycloaddition versus C-H and N-H activation of pyridones and pyrazinones with alkynes: an experimental study

Chemistry. 2007;13(26):7443-65. doi: 10.1002/chem.200601823.

Abstract

The reactivity of a range of pyridone and pyrazinone derivatives towards alkynes in the presence of cyclopentadienylcobaltbis(ethene) has been investigated. Depending on the nature of the substrates, [2+2+2]- or [2+2] cycloaddition, C-H, or N-H activation may occur. In the case of pyridones, the first three predominated with N-protected derivatives, whereas substrates containing N-H bonds followed an N-H activation pathway. The [2+2+2] cycloaddition of an N-butynylisoquinolone was applied successfully to the total synthesis of anhydrolycorinone. Pyrazinone substrates showed similar patterns of reactivity.

Publication types

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

MeSH terms

  • Alkynes / chemistry*
  • Cobalt / chemistry*
  • Crystallography, X-Ray
  • Cyclization
  • Indicators and Reagents
  • Isocyanates / chemistry
  • Models, Molecular
  • Nitriles / chemistry
  • Oxidation-Reduction
  • Pyrazines / chemistry*
  • Pyridones / chemistry*

Substances

  • Alkynes
  • Indicators and Reagents
  • Isocyanates
  • Nitriles
  • Pyrazines
  • Pyridones
  • Cobalt