Exo- and Endohormones XXVI [1]A New Synthesis of (Z)-9-tetradecen-1-yl Acetate, the MainComponent of the Sex Pheromone of the Summer Fruit TortrixMoth Adoxophyes Reticulana (Lepidoptera, Tortricidae)

摘要

A new and practical synthesis of (Z)-9-tetradecen-l-yl acetate was developed using commercially raw material. The synthesis was based on a C8+C2=C_(10)and C_(10)+C4=C_(14) coupling scheme, starting from 1,8-octane-diol. The route involves, as the key step, the use ofthe mercury derivative of the terminal alkyne ω-functionalised as intermediate, which is lithiated and then alkylated. The first coupling reaction took place between monosodium acetylene obtained in situ and l-tert-butoxy-8-bromo-octane. The second coupling reaction consisted in directly lithiated of di(tert-butoxy-dec-9-yne)mercury and then alkylated with 1-bromo-butane obtaining l-tert-butoxy-tetradec-9-yne. After acetylation and stereoselective reduction in the presence of NiP-2 catalyst of l-tert-butoxy-tetradec-9-yne gave (Z)-9-tetradecen-1-yl acetate with 99% isomeric purity.