55830-20-1Relevant academic research and scientific papers
Semiochemicals via epoxide inversion
Oliver, James E.,Waters, Rolland M.
, p. 287 - 294 (2007/10/03)
A sequence of reactions is presented for inverting the configurations of both epoxide carbons in 1,2-disubstituted epoxides. As examples. (+)-disparlure was converted to its enantiomer, (-)-disparlure, and exo-endo conversion of a cyclohexene oxide was de
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 (2007/10/02)
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.
Tritium-Labeled Enantiomers of Disparlure. Synthesis and in Vitro Metabolism
Prestwich, Glenn D.,Graham, Steven McG.,Kuo, Jing-Wen,Vogt, Richard G.
, p. 636 - 642 (2011/07/06)
Both of the enantiomers of disparlure, the gypsy moth sex attractant, have been prepared at high specific activity (58 Ci/mmol) by homogeneous tritiation of the optically active alkenyl oxiranes.An improved preparation of the racemic disparlure is also described.The radiolabeled epoxides are cleanly converted to a single product by enzymes isolated from adult gypsy moths (Lymantria dispar).Enzymatic activity obtained from male antennae showed the highest conversion; enzymes isolated from female antennae and from male and female legs showed lower activity.The identification of the metabolite as the threo-7,8-diol is established by independent synthesis and by chemical derivatizations to the diacetate, n-butylboronate, and bis(trimethylsilyl) ether.A symmetrical epoxide analogous to disparlure is converted to a diol product at a significantly lower rate.
