Rh(I)-catalyzed cyclocarbonylation of allenol esters to prepare acetoxy 4-alkylidenecyclopent-3-en-2-ones

J Org Chem. 2009 Nov 6;74(21):8314-20. doi: 10.1021/jo901459t.

Abstract

A Rh(I)-catalyzed cyclocarbonylation reaction of allenol esters has been examined and its synthetic viability established for the conversion of trisubstituted allenes to bicyclo[4.3.0] and -[5.3.0] skeletons possessing an alpha-acetoxy cyclopentadienone. Tetrasubstituted allenol acetates gave elimination products, providing examples of a cyclocarbonylation reaction between an alkyne and a latent cumulene or cumulene equivalent. Cleavage of the acetate affords a free hydroxyl group illustrating the utility of this method for accessing alpha-hydroxy carbonyls from allenol esters.

Publication types

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

MeSH terms

  • Catalysis
  • Cyclization
  • Cyclopentanes / chemical synthesis*
  • Cyclopentanes / chemistry
  • Esters
  • Ketones / chemistry*
  • Magnetic Resonance Spectroscopy
  • Naphthalenes / chemistry*
  • Rhenium / chemistry*
  • Spectrometry, Mass, Electrospray Ionization

Substances

  • Cyclopentanes
  • Esters
  • Ketones
  • Naphthalenes
  • Rhenium
  • allenolic acid
  • cyclopentenone