Chemistry Institute, State University of Campinas , Campinas, SP, Brazil.
J Nat Prod. 2013 Sep 27;76(9):1559-64. doi: 10.1021/np4001569. Epub 2013 Aug 26.
Four species of gonyleptid harvestmen, Acanthogonyleptes pulcher, Gonyleptes saprophilus (Gonyleptinae), Sodreana barbiellini, and Sodreana leprevosti (Sodreaninae), were examined by GC-MS and ¹³H NMR. All of these species release vinyl ketones, and three of them produce the corresponding pyranyl ketones, which are presumed hetero-Diels-Alder (HDA) dimers. The vinyl ketones 5-methyl-1-hexen-3-one, rac-4-methyl-1-hexen-3-one, and (S)-4-methyl-1-hexen-3-one were synthesized. Natural 4-methyl-1-hexen-3-one is present as a single stereoisomer and has the R-configuration. Vinyl ketone dimers (HDA dimers) were also observed in the scent gland exudate and characterized by HRMS, ¹³C NMR, and ¹H NMR chemical shifts of the pyranyl moiety.
四种长须盲蛛，包括美丽长须盲蛛（Gonyleptinae）、腐食长须盲蛛（Gonyleptes saprophilus）、巴比尔长须盲蛛（Sodreana barbiellini）和莱夫沃斯长须盲蛛（Sodreana leprevosti），被 GC-MS 和 ¹³H NMR 检测。这些物种都释放出乙烯酮，其中三种产生相应的吡喃酮，它们被认为是杂 Diels-Alder (HDA) 二聚体。合成了乙烯酮 5-甲基-1-己烯-3-酮、rac-4-甲基-1-己烯-3-酮和 (S)-4-甲基-1-己烯-3-酮。天然 4-甲基-1-己烯-3-酮仅以单一立体异构体存在，具有 R-构型。乙烯酮二聚体（HDA 二聚体）也存在于香腺分泌物中，并通过高分辨率质谱、¹³C NMR 和吡喃部分的 ¹H NMR 化学位移进行了表征。
