A versatile and convenient protocol for the stereocontrolled synthesis of olefinic insect pheromones.
A combination of the Horner-Emmons synthesis of alkyl 2,4-dienoates with their hydrogenation over complex L.Cr(CO)3 catalysts (L = 3CO or arene) provides a versatile, stereocontrolled and operationally simple approach to the (Z)-disubstituted, (Z)-trisubstituted, (E)-trisubstituted alkenes and skipped (Z,Z)-disubstituted diolefins with a homoallylic type of functionally. This protocol, sometimes supplemented by an enzymatic hydrolysis, was successfully applied to the synthesis of configurationally pure (gp > or = 98%) pheromones of the furniture carpet beetle, dry bean beetle, rusty grain beetle, square-necked grain beetle and a trail-following pheromone mimic for subterranean termites.
Vasil'ev
A A
AA
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation.
Vlasyuk
A L
AL
Gamalevich
G D
GD
Serebryakov
E P
EP
D000475:Alkenes / Q000138:chemical synthesis*; D000818:Animals; D002849:Chromatography, Gas; D001517:Coleoptera / Q000737:chemistry*; D007313:Insecta / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D010675:Pheromones / Q000138:chemical synthesis*
D000475:Alkenes; D010675:Pheromones