81309-86-6Relevant academic research and scientific papers
INSECT PHEROMONES AND THEIR ANALOGS. XXIII. SYNTHESIS OF (7R,8S)-(+)-cis-2-METHYL-7,8-EPOXYOCTADECANE - THE SEX PHEROMONE OF Porthetria dispar
Odinokov, V. N.,Akhmetova, V. R.,Khasanov, Kh. D.,Abduvakhabov, A. A.,Kuchin, A. V.,et al.
, p. 610 - 613 (1989)
A four-stage asymmetric synthesis of (+)-disparlure has been effected from 8-methylnon-2Z-en-1-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 deg C, 20h; H2O, 1h, NaOH, -7 deg C, 30 min) gave 8-methyl-2S,3R-epoxynonan-1-ol (II), which was oxidized (kieselguhr-CrO3-Py, 0 deg C, 2h; 25 deg C, 2h) to 8-methyl-2S,3R-epoxynonan-1-al (III).The coupling of (III) with n-C8H17CH=PPh3 (-78 deg C, 1h; 25 deg C, 15h) gave 2-methyl-7R,8S-epoxy-octadec-9Z-ene (IV), the hydrogenation (H2/5percentPd-C, 25 deg C, 5 days) of which led to (V) in admixture with an isomerzation product.Compound (V) was isolated by HPLC.Substance, yield, D25: (II), 73, -2.75 deg; (III), 80, 80.8 deg; (IV), 50, +37.25 deg; (V), 50, +0.8.The IR and PMR spectra of (II - IV), the 13C NMR spectra of (II) and (III), and the mass spectrum of (IV) are given.
Enantiomer and conformer recognition of (+) and (-)-disparlure and their analogs by the pheromone binding proteins of the gypsy moth, Lymantria dispar
Yu, Yang,Plettner, Erika
supporting information, p. 1811 - 1822 (2013/04/24)
Adult female gypsy moths produce a sex pheromone (+)-(7R,8S)-2-methyl-7,8- epoxyoctadecane, (+)-disparlure, to attract male gypsy moths. To better understand the recognition of (+)-disparlure by the male's olfactory system, we synthesized racemic and enantiopure oxa and thia analogs of (+)-disparlure (ee > 98%). Ab initio calculations of the conformeric landscapes around the dihedral angles C5-6-7-8 and C7-8-9-10 of (+)-disparlure and corresponding dihedral angles of analogs revealed that introduction of the heteroatom changes the conformeric landscape around these important epitopes. The energy difference between HOMO and LUMO decreased after oxygen or sulfur was introduced into the backbone. Consistent with this, an enhancement of binding affinity between sulfur analogs and the pheromone-binding proteins (PBPs) was observed in vitro. Docking of the pheromone and analogs onto models of the two known PBPs of the gypsy moth revealed that the internal binding pocket of PBP1 showed higher selectivity than that of PBP2, consistent with in vitro binding assays. Further energy analysis revealed that enantiomers adopted different conformations with different energies when docked in the internal binding pocket of PBPs, resulting in enantiomer discrimination of PBPs towards disparlure and its analogs.
SYNTHESIS OF (+)-DISPARLURE USING THE REACTION OF 6-METHYLHEPTYL PHENYL SULPHONE WITH TRIMETHYLSILYL ETHYLENE OXIDE AND ASYMMETRIC EPOXIDATION
Marczak, Stanislaw,Masnyk, Marek,Wicha, Jerzy
, p. 2845 - 2846 (2007/10/02)
Lithiated sulphone 2 was reacted with trimethyl(oxiranyl)silane 3 to yield allylic alcohol 4; the latter was epoxidized by the Sharpless procedure and the corresponding hydroxy-epoxide 5b was transformed into (+)-disparlure 6 via tosylate 5c.
SYNTHESES OF OPTICALLY ACTIVE PHEROMONES WITH AN EPOXY RING, (+)-DISPARLURE AND BOTH THE ENANTIOMERS OF (3Z,6Z)-cis-9,10-EPOXY-3,6-HENEICOSADIENE
Mori, Kenji,Ebata, Takashi
, p. 3471 - 3478 (2007/10/02)
(+)-Disparlure 1 and both the enantiomers of (3Z,6Z)-cis-9,10-epoxy-3,6-heneicosadiene 2 were synthesized in optically pure forms employing the Sharpless asymmetric epoxidation as the key-step.The natural pheromone 2 isolated from Estigmene acrea was shown to possess (9S,10R)-stereochemistry.
