Syntheses of optically active pheromones with an epoxy ring, (+)-disparlure and both the enantiomers of (3z,6z)--9,10-epoxy-3,6-heneicosadiene

New Synthesis of the (3Z,6Z,9S,10R)-Isomers of 9,10-Epoxy-3,6-henicosadiene and 9,10-Epoxy-1,3,6-henicosatriene, Pheromone Components of the Female Fall Webworm Moth,Hyphantria cunea

“…The overall yield of 1 was 12% based on 6 (10 steps), this being considerably better than the previous result (7%). 4) The synthesis of (9S,10R)-5 is shown in Scheme 4. The side-chain triene part of 5 was prepared from 3-butyn-1-ol (17), postponing the introduction of the terminal olefin to a later stage of the synthesis.…”

“…The synthesis of (3Z,6Z,9S,10R)-9,10-epoxy-3,6-henicosadiene (1) was first reported by Mori and Ebata in 1986 by employing Sharpless asymmetric epoxidation as the key step. 4) Similarly, by employing the same reaction, (3Z,6Z,9S,10R)-9,10-epoxy-1,3,6-henicosatriene (5) and its lower homolog (4) were synthesized in 1989.…”

“…4) Similarly, by employing the same reaction, (3Z,6Z,9S,10R)-9,10-epoxy-1,3,6-henicosatriene (5) and its lower homolog (4) were synthesized in 1989. 5) In these previous syntheses, the overall yield of 1 was 7% (10 steps), 4) and that of 5 was 1.5% (12 steps).…”

Synthesis of Both the Enantiomers of (6Z,9Z)-cis-3,4-Epoxy-6,9-heptadecadiene, the Pheromone Component of Various Geometrid Moths

“…This colorless oil of 7 was employed in the next step without further purification. (8). A freshly prepared solution of EtMgBr in THF (2.06M, 19.0ml, 39.1 mmol) was added dropwise to a solution of 7 (6.98 g, 39.1 mmol) in dry THF (15 ml) at room temperature under argon.…”

Tissue distribution and substrate specificity of an epoxide hydrase in the gypsy moth,Lymantria dispar

“…An epoxide hydrase (EH) is present in male and female antennae and legs of L. dispar that converts disparlure to the corresponding threo-7,8-diol (4) 1~ Moreover, the male antennal EH produced the threo-(7R,8R)-diol enantiomer stereoselectively; that is ( +)-(7R,8S)-, (-)-(7S,8R)-, and racemic disparlure were all converted to the (7R,8R)-diol with enantiomeric excesses of > 92 % as determined by analysis of the derivatized diols by chiral phase capillary gas chromatography (CP-CGC) 11. In this study, we determined the stereoselectivity of the hydration of racemic disparlure by the EH derived from male antennae (MA), male legs (ML), female antennae (FA), and female legs (FL).…”