Abstract
All four isomers of (Z)-3-cis-6,7-cis-9, 10-diepoxyhenicosenes, 1–4, have been synthesized using D-xylose as the chirally pure starting material. D-Xylose was first converted to 2-deoxy-4,5-O-isopropylidene-3-t-butyldi- methylsilyl-D-threopentose 11, via several steps of selective protection, dehydroxylation, and deprotection. Wittig coupling of 11 with nonyltriphenylphosphonium bromide followed by hydrogenation and acid catalyzed deprotection of hydroxyl groups yielded the chiral (2R,3R)-1,2,3-triol, 14, which was used as the precursor for the C-8 to C-21 unit of the (Z)-3-cis-6,7-cis-9,10-diepoxyhenico- senes. Selective tosylation of 14 followed by stereospecific cyclization yielded (2R,3R)-1,2-epoxytetradecan-3-ol, 16, which was then divergently converted to the t-butyldimethylsilyl ether 17 and tosylate 22, respectively. Establishment of the C-5 through C-7 unit of the target molecules was accomplished via regiospecific coupling of 17 with 1-t-butyldimethylsiloxy-2-propyne to form 18. Stepwise transformation of 18 via the formation of tosylate 19, desilylation, and stereospecific cyclization to form epoxy alcohol 20, followed by P2–Ni reduction yielded a key intermediate, allylic epoxy alcohol (Z)-2-(5S, 6R)-cis-5,6-epoxyheptadecen-1-ol, 21. Similarly, the coupling of 22 with 1-t-butyldimethylsiloxy-2-propyne yielded 23, which was stereospecifically cyclized to form 24. Desilylation and P2–Ni reduction of 24 gave the antipodal intermediate, (Z)-2-(5R, 6S)-cis-5,6-epoxyheptadecen-1-ol, 26. Asymmetric epoxidation of antipodes 21 and 26 with (L)- or (D)-diethyl tartrates resulted in the formation of diepoxy alcohols 27 and 29 from 21, and 33 and 31 from 26, respectively. Tosylation of these diepoxy alcohols followed by coupling with lithium dibutenyl cuprate yielded the four stereoisomers of (Z)-3-cis-6,7-cis-9, 10-diepoxyhenicosenes, 1–4. Analysis of the retention characteristics of these materials revealed that one or both of the S*,R*,S*,R* stereoisomers comprise the major pheromone component(s) of Leucoma salicis.
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Wimalaratne, P.D.C., Slessor, K.N. Chiral Synthesis of (Z)-3-cis-6,7-cis-9, 10-Diepoxyhenicosenes, Sex Pheromone Components of the Satin Moth, Leucoma salicis . J Chem Ecol 30, 1225–1244 (2004). https://doi.org/10.1023/B:JOEC.0000030274.73355.b8
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DOI: https://doi.org/10.1023/B:JOEC.0000030274.73355.b8