Jones T H, Laddago A, Don A W, Blum M S
Laboratory of Chemistry, National Heart, Lung and Blood Institute, Bethesda, Maryland 20892.
J Nat Prod. 1990 Mar-Apr;53(2):375-81. doi: 10.1021/np50068a016.
The alkaloidal venom of Monomorium smithii was found to contain (5E,9Z)-3-butyl-5-(4-penten-1-yl)indolizidine [1b], a novel indolizidine, its monocyclic analogue trans-2-butyl-5-(8-nonen-1-yl)pyrrolidine [2], (5E,8Z)-3,5-di(5-hexen-1-yl)pyrrolizidine [3], and trans-2-(5-hexen-1-yl)-5-(8-nonen-1-yl)pyrrolidine [4]. The structure of 1b was based on the results of two independent syntheses. Reductive amination of the appropriate triketone confirmed the carbon-nitrogen skeleton of 1b and suggested its stereochemistry, which was verified by the results of a stereoselective synthesis based on pyrrole hydrogenation. The chemotaxonomic implications of this first report of the concomitance of a 3,5-dialkylindolizidine and a 3,5-dialkylpyrrolizidine in an ant venom are discussed.
已发现史密斯氏猛蚁的生物碱毒液含有(5E,9Z)-3-丁基-5-(4-戊烯-1-基)中氮茚[1b]，一种新型中氮茚，其单环类似物反式-2-丁基-5-(8-壬烯-1-基)吡咯烷[2]，(5E,8Z)-3,5-二(5-己烯-1-基)吡咯嗪[3]，以及反式-2-(5-己烯-1-基)-5-(8-壬烯-1-基)吡咯烷[4]。1b的结构基于两个独立合成的结果。适当三酮的还原胺化反应证实了1b的碳氮骨架并表明了其立体化学，基于吡咯氢化的立体选择性合成结果验证了该立体化学。本文讨论了在一种蚂蚁毒液中首次报道的3,5-二烷基中氮茚和3,5-二烷基吡咯嗪共存的化学分类学意义。
