Synthesis and field evaluation of stereoisomers and analogues of 5-methylheptadecan-7-ol, an unusual sex pheromone component of the lichen moth, Miltochrista calamine.
Synthesis and field evaluation of stereoisomers and analogues of 5-methylheptadecan-7-ol, an unusual sex pheromone component of the lichen moth, Miltochrista calamine.
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5-甲基十七烷-7-醇立体异构体和类似物的合成和现场评估，5-甲基十七烷-7-醇是地衣蛾 Miltochrista calamine 的一种不寻常的性信息素成分。
DOI：
10.1007/s10886-014-0405-5
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
and Tetsu ANDO
中科院分区：
文献类型：
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作者：
Yuta MURAKI;Tomonori TAGURI;Rei YAMAKAWA;and Tetsu ANDO
地衣蛾Miltochrista calamina(Arctiidae，Lithosiinae)的雌性此前被证明产生5-甲基十七烷-7-醇(1)作为性信息素。在现场测试中，雄性只被四种立体异构体的(5R，7R)-异构体所吸引，这四种立体异构体是从两种非对映异构体混合物中分离出来的。以光学活性的二次对甲苯磺酸盐的SN2反应和环氧化物中间体的雅各布森水解动力学拆分为关键步骤，开发了以(S)-环氧丙烷为起始原料合成(5R，7R)-1的新路线。对产物和由(R)-环氧丙烷合成的对映体进行了对映体选择性的高效液相色谱分析，证实了它们的高对映体过量(>；99%)。利用这种立体定向合成方法，合成了6个与(5R，7R)-1构型相同但不同烷基连接中心的类似物(S)，以获得GC/MS数据并考察其构效关系。鱿鱼类来区分它们。合成的类似物的质谱图显示，除了羟基以外，甲基周围也有裂解产生的特征碎片离子。在野外诱捕试验中，六种化合物中有五种对马伦有吸引力。Calamamoths，这表明雄性区别了甲基和羟基的配置，但较少能够感知信息素中两个烷基链的长度差异。
Females of the lichen moth,Miltochrista calamina(Arctiidae, Lithosiinae), were previously shown to produce 5-methylheptadecan-7-ol (1) as a sex pheromone. In field tests, males were attracted only by the (5R,7R)-isomer of the four stereoisomers that were prepared by separation from two mixtures of diastereoisomers. A new route to (5R,7R)-1starting from (S)-propylene oxide was developed utilizing the SN2 reaction of an optically active secondary tosylate and the Jacobsen hydrolytic kinetic resolution of an epoxide intermediate as key steps. Enantioselective HPLC analysis of the product and the antipode synthesized from (R)-propylene oxide confirmed their high enantiomeric excess (> 99 %). Using this stereospecific synthesis, six analogues with the same configuration as (5R,7R)-1but with different alkyl chain(s) connected to the stereogenic centers were prepared in order to obtain GC/MS data and to examine the ability ofM. calaminamales to discriminate between them. The mass spectra of the synthetic analogues revealed characteristic fragment ions derived by cleavage around the methyl group in addition to that at the hydroxyl group. In field trapping tests, five out of the six compounds were attractive to maleM. calaminamoths, indicating that the males distinguished the configurations of methyl and hydroxyl groups but were less able to perceive differences in the lengths of the two alkyl chains in the pheromone.