1988 年 46 巻 2 号 p. 108-120
It has been known that females of the American cockroach, Periplaneta americana L. produce potent sex excitant and attractant pheromone. Extensive efforts have been made to isolate, characterize and synthesize its active components along with biochemical and behavioral studies for over 30 years, and culminated in several total syntheses of the major sex pheromone, periplanone-B with potent activity (threshold : 10-13g). These syntheses can be devided into two classes by the strategy on the preparation of its skeleton, germacrene-type ten-membered ring system; the use of oxy-Cope rearrangement or the intramolecular alkylation. This review deals mainly with these syntheses especially focussing on practically first synthesis of optically active periplanone-B by us. Proper base treatment of substituted α-phenylthioacrylate gave the desired cyclodecene ring system in good yield and reductive elimination of vicinal phenylthio-benzoate with sodium naphthalenide cleanly gave the conjugated diene. Including these key steps, the synthesis was accomplised in overall 0.5% yield through 28 steps.