Phosphine-catalyzed cycloadditions of allenic ketones: new substrates for nucleophilic catalysis

J Org Chem. 2007 Feb 2;72(3):1051-4. doi: 10.1021/jo062170l.

Abstract

A range of phosphine-catalyzed cycloaddition reactions of allenic ketones have been studied, extending the scope of these processes from the more widely used 2,3-butadienoates to allow access to a number of synthetically useful products. Reaction of allenyl methyl ketone 4 with exo-enones afforded spirocyclic compounds in good regioselectivity and promising enantioselectivity via a [2 + 3] cycloaddtion. Aromatic allenyl ketones undergo a phosphine-promoted dimerization to afford functionalized pyrans, leading to a formal [2 + 4] Diels-Alder product, but did not react in the [2 + 3] cycloaddition. The results from other reactions that had found utility with 2,3-butadienoates are also reported.

MeSH terms

  • Alkadienes / chemical synthesis*
  • Butadienes / chemistry
  • Catalysis
  • Cyclization
  • Ketones / chemical synthesis*
  • Models, Chemical
  • Phosphines / chemistry*

Substances

  • Alkadienes
  • Butadienes
  • Ketones
  • Phosphines
  • propadiene
  • phosphine