Synthesis of disparlure analogues, using resolution on microcrystalline cellulose triacetate-I

• Published in: Tetrahedron: asymmetry Vol. 16; no. 23; pp. 3773 - 3784
• Main Authors: Inkster, James A.H., Ling, Ivy, Honson, Nicolette S., Jacquet, Loïc, Gries, Regine, Plettner, Erika
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 28.11.2005; Elsevier
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Chemistry, Physical; Physical Sciences; Science & Technology; PERFORMANCE LIQUID-CHROMATOGRAPHY; PHEROMONE-BINDING-PROTEINS; LYMANTRIA-DISPAR; DISCRIMINATION; GYPSY-MOTH; ENANTIOMERS; CHIRAL EPOXY ALCOHOLS; ALPHA; (-)-DISPARLURE; (+)-DISPARLURE
• ISSN: 0957-4166; 1362-511X
• DOI: 10.1016/j.tetasy.2005.10.031

The gypsy moth, Lymantria dispar, uses a chiral epoxide, (+)-(7 R,8 S)-2-methyl-7,8-epoxyoctadecane, (+)-disparlure, as its main sex attractant. The moths can detect both enantiomers of disparlure and respond differently to each one. In an effort to understand the structure–activity relationships of the gypsy moth olfactory system, we prepared the analogues of (+)- and (−)-disparlure. The key intermediate in route to the analogues was 2-epoxytridecan-1-ol. Herein we report the resolution of 2-epoxytridecan-1-yl esters on microcrystalline cellulose triacetate and the synthesis of 5-oxa and (5 Z)-ene analogues of (+)- and (−)-disparlure. An effort to make 5-aza analogues resulted in the formation of anti-5-(1-hydroxy-1-undecyl)-3-(3-methylbutyl)oxazolidin-2-one. The analogues were tested for their electroantennogram responses and for their ability to bind to pheromone-binding protein 1 (PBP1). We found that the 5-oxa analogues gave strong responses and that the antenna and the PBP1 no longer distinguish the enantiomers of the 5-oxa analogues. The analogues all bound the PBP1 with similar affinity to (−)-disparlure.