Synthesis of sub-units of marine polycyclic ethers by ring-closing metathesis and hydroboration of enol ethers

Article abstract of DOI:10.1016/S0040-4020(99)00295-1

A novel syntheses of Z-5-dezenol, Z-5-decenyl acetate, Z-7-dodecenol, Z- 7-dodecenyl acetate, Z-9-tricosene, Z-7,8-epoxy-methyloctadecane which are sex pheromone components of Lepidoptera and Diptera orders, have been realized via stereoselective cometathesis of 1,5-cyclooctadiene with ethylene in the presence of MoCls/SiO₂-SnMe₄ as a key reaction. The male cometathesis product, 1,Z-5,9-decatriene, has been converted into pheromone components monocloned above by regioselective partial hydroboration or hydrozirconation with help of 9-BBN and Cp₂ZrHCl, correspondingly. The protonolysis of the obtained zirconosene derivative gave 1,Z-5-decadiene. Hydroboration-oxidation or hydroboration-C₂-homologation of the latter but 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 derivative with convenient lithium cuprates resulted in Z-9- tricosene, the main sex pheromone component of House Fly (Musca Domestica), or in 2-methyl-Z-7-octadecene, the presence of Gypsy Moth (Lymantria Dispar) sex attractant.