Four new bioactive manzamine-type alkaloids from the Philippine marine sponge Xestospongia ashmorica
Four new bioactive manzamine-type alkaloids from the Philippine marine sponge Xestospongia ashmorica
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DOI：
10.1021/np9604083
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发表时间：
1996-11-01
影响因子：
5.1
通讯作者：
VanSoest, RWM
中科院分区：
文献类型：
--
作者：
Edrada, RA;Proksch, P;VanSoest, RWM
对菲律宾海绵Xestospongia ashmorica的分析发现了四个新的甘露糖同系物1-4和四个已知化合物5和7-9。化合物1是甘露糖胺X的6-脱氧衍生物，而2-4是甘露糖胺J(5)、3，4-二氢甘露糖胺A(6)和甘露糖胺A(7)的N-氧化物。新化合物的结构是根据核磁共振波谱(H-1，C-13，COSY，H-1检测到的直接和远程C-13-H-1关联)和质谱学(EI，FAB-MS和电喷雾电离)数据明确确定的。生物碱N-氧化物结构经锌/盐酸还原转化为相应的叔碱得到确证。这是首次报道在海绵中发现具有生物活性的甘露糖胺N-氧化物。化合物7对杂食性害虫斜纹夜蛾幼虫具有一定的杀虫活性(ED50为35ppm)。化合物7对革兰氏阳性菌枯草芽孢杆菌和金黄色葡萄球菌也有抑制作用。用L1578y小鼠淋巴瘤细胞进行体外细胞毒试验。在所研究的生物碱中，N-氧化物3和4的活性最强(ED50=1.6mU g/mL)，其次是化合物7(ED50=1.8mU g/mL)。
Analysis of the Philippine marine sponge Xestospongia ashmorica afforded four new manzamine congeners 1-4 and four known compounds 5 and 7-9. Compound 1 is the 6-deoxy derivative of manzamine X, while 2-4 are the N-oxides of manzamine J (5), 3,4-dihydromanzamine A (6), and manzamine A (7), respectively. The structures of the new compounds were unambiguously established on the basis of NMR spectroscopic (H-1, C-13, COSY, H-1-detected direct, and long-range C-13-H-1 correlations) and mass spectrometric (EI, FAB-MS, and electrospray ionization) data. Alkaloid N-oxide structures were confirmed by conversion to the corresponding tertiary bases by reduction with Zn/HCl. This is the first report of the occurrence of bioactive manzamine N-oxides in marine sponges. Compound 7 exhibited insecticidal activity toward neonate larvae of the polyphagous pest insect Spodoptera littoralis (with an ED50 of 35 ppm) when incorporated in artificial diet and offered to larvae in a chronic feeding bioassay. Compound 7 was also active against the Gram-positive bacteria Bacillus subtilis and Staphylococcus aureus. Cytotoxicity was studied in vitro using L1578y mouse lymphoma cells. From the alkaloids studied, the N-oxides 3 and 4 were the most active (ED50 = 1.6 mu g/mL) followed by compound 7 (ED50 = 1.8 mu g/mL).