Improved synthesis and deployment of (2S,3R)-2-(2Z,5Z-octadienyl)-3-nonyloxirane, a pheromone of the pink moth, Lymantria mathura.
We report two new syntheses of (2S,3R)-2-(2Z,5Z-octadienyl)-3-nonyloxirane, the main sex pheromone component of the pink moth, Lymantria mathura. The key step in the first route was the construction of (Z,Z)-1-bromo-1,4-heptadiene (6), which was coupled in the final step with 2-iodomethyl-3-nonyloxirane 4 via a Grignard reaction. The second approach employed alkylation of 1,4-heptadiynyllithium with epoxy triflates 7 in ether/hexane and provided the pheromone in >/=37% overall yield from alcohol 2. The 4:1 ratio of pheromone enantiomers, reportedly the most attractive to pink moth males, can be directly crafted from appropriately selected Sharpless asymmetric epoxidation conditions.
Khrimian
Ashot
A
Chemicals Affecting Insect Behavior Laboratory, BARC-West, PSI, ARS, USDA, Beltsville, Maryland 20705, USA. khrimiaa@ba.ars.usda.gov
Oliver
James E
JE
Hahn
Roger C
RC
Dees
Nikki H
NH
White
Jeff
J
Mastro
Victor C
VC
D000818:Animals; D005027:Ethylene Oxide / Q000031:analogs & derivatives / Q000138:chemical synthesis* / Q000737:chemistry; D005227:Fatty Acids / Q000138:chemical synthesis* / Q000737:chemistry; D007300:Insect Control / Q000379:methods; D008297:Male; D009036:Moths / Q000502:physiology*; D010675:Pheromones; D012724:Sex Attractants / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
C487532:(2S,3R)-2-(2Z,5Z-octadienyl)-3-nonyloxirane; D005227:Fatty Acids; D010675:Pheromones; D012724:Sex Attractants; C010411:insect attractants; D005027:Ethylene Oxide