SYNTHESES OF THE FEMALE SEX-PHEROMONES OF MATSUCOCCUS PINE SCALES USING THE [2,3]-WITTIG REARRANGEMENT OF A BISALLYLIC TERTIARY ETHER

A convergent, general synthesis of 2E,4E)-4,6,10,12-tetramethyltrideca -2,4-dien-7-one (matsuone, 1) and five closely related analogs (2-6), which serve as sex pheromone components of female Matsucoccus pine sca les, is described. The aldehydes 8a and 8b were obtained via a reactio n sequence in which the key step is a [2,3]-Wittig sigmatropic rearran gement of the oxazoline ether of bisallylic tertiary alcohol 11. Coupl ing of 8 with the appropriate nucleophilic reagents, followed by oxida tion of the resultant secondary alcohols, afforded the pheromone compo nents 1-6.