P(RNCH(2)CH(2))(3)N-catalyzed 1,2-addition reactions of activated allylic synthons.
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.
Kisanga
Philip B
PB
Department of Chemistry, Iowa State University, Ames, Iowa 50010, USA.
Verkade
John G
JG
D000447:Aldehydes / Q000138:chemical synthesis / Q000737:chemistry; D001952:Bridged-Ring Compounds / Q000737:chemistry; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods; D002855:Chromatography, Thin Layer; D004952:Esters / Q000737:chemistry; D006574:Heterocyclic Compounds, 2-Ring / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013696:Temperature
D000447:Aldehydes; D001952:Bridged-Ring Compounds; D004952:Esters; D006574:Heterocyclic Compounds, 2-Ring; D009570:Nitriles; D009943:Organophosphorus Compounds; C449943:P(CH(3)NCH(2)CH(2))(3)N