P(RNCH(2)CH(2))(3)N-catalyzed 1,2-addition reactions of activated allylic synthons

J Org Chem. 2002 Jan 25;67(2):426-30. doi: 10.1021/jo0106492.

Abstract

Activated allylic compounds of the type RCH:CHCH(2)Z (Z = CN, CO(2)Me) react efficiently with aromatic aldehydes in the presence of 20-40 mol % of P(R'NCH(2)CH(2))(3)N at -94 to -63 degrees C. Both R = H and R = Me lead exclusively to alpha-addition products. When R = H and Z = CN, an allylic transposition occurs to afford a Baylis-Hillman product as the only product.

Publication types

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

MeSH terms

  • Aldehydes / chemical synthesis
  • Aldehydes / chemistry
  • Bridged-Ring Compounds / chemistry
  • Catalysis
  • Chemistry, Organic / methods
  • Chromatography, Thin Layer
  • Esters / chemistry
  • Heterocyclic Compounds, 2-Ring / chemistry
  • Magnetic Resonance Spectroscopy
  • Molecular Structure
  • Nitriles / chemical synthesis*
  • Nitriles / chemistry*
  • Organophosphorus Compounds / chemistry*
  • Oxidation-Reduction
  • Stereoisomerism
  • Temperature

Substances

  • Aldehydes
  • Bridged-Ring Compounds
  • Esters
  • Heterocyclic Compounds, 2-Ring
  • Nitriles
  • Organophosphorus Compounds
  • P(CH(3)NCH(2)CH(2))(3)N