Stereospecific Pd(0)-catalyzed arylation of an allylic hydroxy phosphonate derivative: formal synthesis of (S)-(+)-ar-turmerone

J Org Chem. 2003 Nov 28;68(24):9502-5. doi: 10.1021/jo0351318.

Abstract

Reaction of the (1S)-allylic hydroxy phosphonate 1(S) with methyl chloroformate in pyridine yields the corresponding carbonate 3(S). The carbonate 3(S) undergoes a palladium-catalyzed arylation with p-tolyl tributylstannane to give both the 1E and 1Z vinyl phosphonates 6 (85:15). The E and Z vinyl phosphonates 6 were shown to have the opposite configuration at C-3. The major vinyl phosphonate isomer (3S,1E), was converted to (3S)-3-(p-tolyl)-butanal 8(S), completing a formal total synthesis of (S)-ar-turmerone 5a.

Publication types

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

MeSH terms

  • Allyl Compounds / chemical synthesis*
  • Allyl Compounds / chemistry
  • Catalysis
  • Ketones / chemical synthesis*
  • Ketones / chemistry
  • Models, Chemical
  • Molecular Structure
  • Organophosphonates / chemical synthesis*
  • Organophosphonates / chemistry
  • Palladium / chemistry*
  • Sesquiterpenes
  • Stereoisomerism
  • Structure-Activity Relationship
  • Toluene / analogs & derivatives*
  • Toluene / chemical synthesis*
  • Toluene / chemistry

Substances

  • Allyl Compounds
  • Ketones
  • Organophosphonates
  • Sesquiterpenes
  • ar-turmerone
  • Toluene
  • Palladium