Khrimian Ashot, Shirali Shyam, Vermillion Karl E, Siegler Maxime A, Guzman Filadelfo, Chauhan Kamlesh, Aldrich Jeffrey R, Weber Donald C
US Department of Agriculture, Agricultural Research Service, Invasive Insect Biocontrol and Behavior Laboratory, Beltsville, MD, 20705, USA,
J Chem Ecol. 2014 Dec;40(11-12):1260-8. doi: 10.1007/s10886-014-0521-2. Epub 2014 Nov 19.
Preparation of a complete stereoisomeric library of 1,10-bisaboladien-3-ols and selected 10,11-epoxy-1-bisabolen-3-ols was pivotal for the identification of the aggregation pheromone of the brown marmorated stink bug, Halyomorpha halys. Herein, we describe syntheses of the remaining 10,11-epoxy-1-bisabolen-3-ols, and provide additional evidence on the assignment of relative and absolute configurations of these compounds by single-crystal X-ray crystallography of an intermediate, (3S,6R,7R,10S)-1-bisabolen-3,10,11-triol. To demonstrate the utility of this stereoisomeric library, we revisited the aggregation pheromone of the harlequin bug, Murgantia histrionica, and showed that the male-produced pheromone consists of two stereoisomers of 10,11-epoxy-1-bisabolen-3-ol. Employment of eight cis-10,11-epoxy-1-bisabolen-3-ol stereoisomeric standards, two enantioselective GC columns, and NMR spectroscopy enabled the identification of these compounds as (3S,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol and (3S,6S,7R,10R)-10,11-epoxy-1-bisabolen-3-ol, which are produced by M. histrionica males in 1.4:1 ratio.
制备1,10 - 双环倍半水芹烯 - 3 - 醇和选定的10,11 - 环氧 - 1 - 双环倍半水芹烯 - 3 - 醇的完整立体异构体文库对于鉴定褐边绿刺蛾（Halyomorpha halys）的聚集信息素至关重要。在此，我们描述了其余10,11 - 环氧 - 1 - 双环倍半水芹烯 - 3 - 醇的合成，并通过中间体(3S,6R,7R,10S) - 1 - 双环倍半水芹烯 - 3,10,11 - 三醇的单晶X射线晶体学，为这些化合物的相对和绝对构型的归属提供了额外证据。为了证明该立体异构体文库的实用性，我们重新研究了小丑蝽（Murgantia histrionica）的聚集信息素，并表明雄性产生的信息素由10,11 - 环氧 - 1 - 双环倍半水芹烯 - 3 - 醇的两种立体异构体组成。使用八种顺式 - 10,11 - 环氧 - 1 - 双环倍半水芹烯 - 3 - 醇立体异构体标准品、两根对映体选择性气相色谱柱和核磁共振光谱，确定这些化合物为(3S,6S,7R,10S) - 10,11 - 环氧 - 1 - 双环倍半水芹烯 - 3 - 醇和(3S,6S,7R,10R) - 10,11 - 环氧 - 1 - 双环倍半水芹烯 - 3 - 醇，它们由小丑蝽雄性以1.4:1的比例产生。
Zotero 插件