著者

武口 俊太 川岸 貴博 伊藤 久央 井口 和男

出版者

日本薬学会化学系薬学部会

雑誌

反応と合成の進歩シンポジウム 発表要旨概要

巻号頁・発行日

vol.31, pp.22, 2005

---

Clavubicyclone, a novel clavulone-related marine prostanoid, was isolated from Okinawan soft coral Clavularia viridis by our group. To determine the absolute stereochemistry of clavubicyclone, development of the total synthetic route was performed. The key step of our synthetic route was construction of bicyclo[3.2.1]octane skeleton by Cope rearrangement of the divinylcyclopropane derivative. The substrate of Cope rearrangement was prepared from cis-2-butene-1,4-diol as a starting material through carbon chain elongation reactions and the rhodium catalyzed intramolecular cyclopropanation reaction. The Cope rearrangement smoothly proceeded by heating the divinylcyclopropane derivative in diphenyl ether (180 °C) to give the desired bicyclo[3.2.1]octane derivative. We are examining to convert the rearrangement product to clavubicyclone.

著者

渋谷 厚輝 武口 俊太 伊藤 久央 井口 和男

出版者

日本薬学会化学系薬学部会

雑誌

反応と合成の進歩シンポジウム 発表要旨概要

巻号頁・発行日

vol.34, pp.144, 2008

---

Clavubicyclone was isolated from Okinawan soft coral, Clavularia viridis, by our group as a novel prostanoid-related compound. The absolute stereochemistry and biological activity of clavubicyclone have not yet been examined due to small quantities of isolated samples. We recently achieved the total synthesis of clavubicyclone as a racemic form through Cope rearrangement as a key step. However, there are several problems on our previous synthetic route; improvement of the yield of Cope rearrangement and shortening of the relatively longer sequence. To overcome these problems and to achieve an enantioselective synthesis, we examined further synthetic research. Cope rearrangement was proceeded smoothly by changing the stereochemistry of the substrate. We also achieved to obtain an intermediate as an optically active form by using enantioselective Mukaiyama aldol reaction. Introduction of side chains to an optically active bicyclo[3.2.1]octane skeleton is now underway.