Asymmetric Synthesis of (5R,6S)-6-Acetoxy-5-hexadecanolide, the Major Component of the Oviposition Attractant Pheromone of the Mosquito Culex pipens fatigans, and Two of Its Stereoisomers

Article abstract of DOI:10.1021/jo00376a056

The benzyl derivatives of (R)- and (S)-2-hydroxydodecanal have been prepared by a previously described asymmetric synthesis based on a chiral 1,3-oxathiane and have been converted into (5R,6S)-6-acetoxy-5-hexadecanolide, a mosquito oviposition attractant pheromone, and its 5R,6R and 5S,6R stereoisomers in highly diastereoselective fashion.The steps involved are Grignard addition of 5-pentenylmagnesium bromide, Mitsunobu inversion for one of the erythro (5R,6S) isomers and oxidation-hydride reduction for the other, ozonization, oxidation, lactone formation, debenzylation, and acetylation, the overall yield in these steps being 30-42percent.