来自瓢虫的聚氮杂大环内酯：环大小选择性低聚反应
Polyazamacrolides from ladybird beetles: ring-size selective oligomerization.
作者信息
Schroeder F C, Smedley S R, Gibbons L K, Farmer J J, Attygalle A B, Eisner T, Meinwald J
机构信息
Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853, USA.
出版信息
Proc Natl Acad Sci U S A. 1998 Nov 10;95(23):13387-91. doi: 10.1073/pnas.95.23.13387.
The pupal defensive secretion of the 24-pointed ladybird beetle, Subcoccinella vigintiquatuorpunctata, consists of a mixture of macrocyclic polyamines, dominated by the three dimeric, 30-membered macrocycles 11-13, derived from the two building blocks 11-(2-hydoxyethylamino)-5-tetradecenoic acid (9) and 11-(2-hydoxyethylamino)-5,8-tetradecadienoic acid (10). Smaller amounts of the four possible cyclic trimers of 9 and 10 were also detected, corresponding to 45-membered macrocycles. Structural assignments were based on NMR-spectroscopic investigations and HPLC-MS analyses. In addition, the all-S absolute configuration of the S. vigintiquatuorpunctata macrocycles was determined by comparison of derivatives of the natural material with enantiomerically pure synthetic samples. Comparing this alkaloid mixture with that of the pupal defensive secretion in related ladybird beetle species indicates that the degree of oligomerization of the 2-hydroxyethylamino carboxylic acid building blocks can be carefully controlled by the insects.
二十四斑瓢虫（Subcoccinella vigintiquatuorpunctata）蛹期的防御分泌物由大环多胺混合物组成，主要成分是三种二聚体、30元大环化合物11 - 13，它们由两种结构单元11-(2 - 羟乙基氨基)-5 - 十四碳烯酸（9）和11-(2 - 羟乙基氨基)-5,8 - 十四碳二烯酸（10）衍生而来。还检测到了少量由9和10形成的四种可能的环状三聚体，对应于45元大环化合物。结构归属基于核磁共振光谱研究和高效液相色谱 - 质谱分析。此外，通过将天然物质的衍生物与对映体纯的合成样品进行比较，确定了二十四斑瓢虫大环化合物的全S绝对构型。将这种生物碱混合物与相关瓢虫物种蛹期防御分泌物的混合物进行比较表明，昆虫可以精细地控制2 - 羟乙基氨基羧酸结构单元的低聚程度。
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