Synthesis of Z-isomeric insect sex pheromone components via ethenolysis of1,5-cyclooctadiene

A novel syntheses of Z-5-decenol, Z-5-decenyl acetate, Z-7-dodecenol, Z-7-d odecenyl acetate, Z-9-tricosene, Z-7,8-epoxy-2-methyloctadecane which are s ex pheromone components of Lepidoptera and Diptera orders, have been realiz ed via stereoselective cometathesis of 1,5-cyclooctadiene with ethylene in the presence of MoCl5/SiO2-SnMe4 as a key reaction. The main cometathesis p roduct, 1,Z-5,9-decatriene, has been converted into pheromone components me ntioned above by regioselective partial hydroboration or hydrozirconation w ith help of 9-BBN and Cp2ZrHCl, correspondingly. The protonolysis of the ob tained zirconosene derivative gave 1,Z-5-decadiene. Hydroboration-oxidation or hydroboration-Cz-homologation of the latter led to Z-5- or Z-7 monoene pheromone components. Hydroboration-iodination of terminal double bond in 1 ,Z-5,9-decatriene, and further cross-coupling of the obtained iodine deriva tive with convenient lithium cuprates resulted in Z-9-tricosene, the main s ex pheromone component of House Fly ( Musca Domestica), or in 2-methyl-Z-7- octadecene, the precursor of Gypsy Moth (Lymantria Dispar) sex attractant. (C) 1999 Elsevier Science Ltd. All rights reserved.