著者

春沢 信哉 栗原 拓史

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.53, no.8, pp.712-723, 1995-08-01 (Released:2009-11-16)

参考文献数

36

被引用文献数

4 5

---

A highly stereoselective synthesis of (Z) - or (E) -double bonds in 10-membered thiolcarbonates is achieved by the [3, 3] sigmatropic rearrangement of 8-membered thionocarbonates which proceeds through the chairlike vs. boatlike transition states. The formation of the 8-membered intermediates followed by their [3, 3] sigmatropic rearrangements were investigated by experiments and theoretical calculations. Their utilities of this methodology have been demonstrated by the unique and stereoselective synthesis of (-)-yellow scale pheromone. Moreover, medium-membered heterocyclic allenes were synthesized by this method. The structure and reactivity of a new type of strained 8-membered allene were also examined. Using this method combined with a novel application of the newly developed SmI2-HMPA reduction of the cyclic allene, the antifungal constituent of a Sapium japonicum was synthesized.