Insect pheromones and their analogs

XXIII. Synthesis of (7R,8S)-(+)-cis-2-methyl-7,8-epoxyoctadecane — The sex pheromone of Porthetria dispar


A four-stage asymmetric synthesis of (+)-disparlure [(7R,8S)-(+)-cis-methyl-7,8-epoxyoctadecane (V)] has been effected from 8-methylnon-2Z-en-l-ol (I), obtained by the carboalumination of acetylene with tris(5-methylhexyl)aluminum using the Sharpless reaction. The asymmetric epoxidation of (I), (Ar, mol. sieve A, (+)-DET, (iOPr)4Ti, t-BuOOH, −15°C, 20 h; H2O, 1 h, NaOH, −7°C, 30 min) gave 8-methyl-2S,3R-epoxynonan-l-ol (II), which was oxidized (kieselguhr-CrO3-Py, 0°C, 2 h; 25°C, 2 h) to 8-methyl-2S,3R-epoxynonan-l-al (III). The coupling of (III) with n-C8H17CH=PPh3 (−78°C, 1 h; 25°C, 15 h) gave 2-methyl-7R,8S-epoxyoctadec-9Z-ene (IV), the hydrogenation (H2/5% Pd-C, 25°C, 5 days) of which led to (V) in admixture with an isomerization product. Compound (V) was isolated by HPLC. Substance, yield, [α] 25D : (II), 73, −2.75°; (III), 80, [80.8°; (IV), 50, +37.25°; (V), 50, +0.8°. The IR and PMR spectra of (II–IV), the13C NMR spectra of (II) and (III), and the mass spectrum of (IV) are given.

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Additional information

Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 715–718, September–October, 1989.

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Odinokov, V.N., Akhmetova, V.R., Khasanov, K.D. et al. Insect pheromones and their analogs. Chem Nat Compd 25, 610–613 (1989).

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  • Gossypol
  • Allyl Alcohol
  • Insect Pheromone
  • Epoxyalcohol
  • Asymmetric Epoxidation