Taguri Tomonori, Yamakawa Rei, Adachi Yasushi, Mori Kenji, Ando Tetsu
Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Japan.
Biosci Biotechnol Biochem. 2010;74(1):119-24. doi: 10.1271/bbb.90639. Epub 2010 Jan 7.
Female moths of Lyclene dharma dharma (Arctiidae, Lithosiinae) produce a novel sex pheromone composed of three methyl-branched ketones: 6-methyl-2-octadecanone (I), 14-methyl-2-octadecanone (II), and 6,14-dimethyl-2-octadecanone (III). Their structures were confirmed by syntheses accomplished by a different route for each component. In order to obtain a sufficient amount of the synthetic pheromone, we developed new routes via methyl-branched 1-alkenes: 6-methyl-1-octadecene (1), 14-methyl-1-octadecene (2), and 6,14-dimethyl-1-octadecene (3). Compound 1 was synthesized by coupling between a C(10)-chain bromide and a 3-methyl-branched C(8) unit (A) prepared from 3-methyl-1,5-pentanediol, 2, by coupling between a C(11)-chain bromide and a 3-methyl-branched C(7) unit (B) prepared from 2-hexanone, and 3, by connecting A and B, using propargyl alcohol as a C(3) linchpin. The use of 3-chloro-1-propanol and tert-butyl acetoacetate as the linchpin was also examined to connect the two synthetic blocks in the synthesis of 3. Components I-III were obtained by Wacker oxidation of the corresponding 1-alkenes 1-3 in good yields.
达摩茸毒蛾（灯蛾科，锂蛾亚科）的雌蛾会产生一种由三种甲基支链酮组成的新型性信息素：6-甲基-2-十八烷酮（I）、14-甲基-2-十八烷酮（II）和6,14-二甲基-2-十八烷酮（III）。通过对每种成分采用不同路线进行合成，确认了它们的结构。为了获得足够量的合成信息素，我们开发了通过甲基支链1-烯烃的新路线：6-甲基-1-十八碳烯（1）、14-甲基-1-十八碳烯（2）和6,14-二甲基-1-十八碳烯（3）。化合物1是通过C(10)链溴化物与由3-甲基-1,5-戊二醇制备的3-甲基支链C(8)单元（A）偶联而成；2是通过C(11)链溴化物与由2-己酮制备的3-甲基支链C(7)单元（B）偶联而成；3是通过使用炔丙醇作为C(3)连接键连接A和B而成。还研究了使用3-氯-1-丙醇和乙酰乙酸叔丁酯作为连接键在3的合成中连接两个合成模块。通过对相应的1-烯烃1-3进行瓦克氧化，以良好的产率获得了成分I-III。
