Five new alkaloids from the tropical ascidian, Lissoclinum sp. lissoclinotoxin A is chiral
Five new alkaloids from the tropical ascidian, Lissoclinum sp. lissoclinotoxin A is chiral
复制标题
来自热带海鞘 Lissoclinum sp 的五种新生物碱。
DOI：
10.1021/jo00101a018
复制
发表时间：
1994
影响因子：
3.6
通讯作者：
T. Molinski
中科院分区：
文献类型：
--
作者：
P. A. Searle;T. Molinski
从 lissoclin A (1)、lissoclin B (2)、lissoclin C (3)、lissoclinotoxin C (5) 和二聚 lissoclinotoxin D (6) 以及已知化合物 lissoclinotoxin A (4)、2-苯乙胺 (11) 和 6-溴色胺 (12) 中分离出五种新生物碱Lissoclinum sp.采自澳大利亚大堡礁。 Lissoclin A (1) 经过光重排，生成新的苯并-1, 3-恶噻唑啉 10。首次报道了 4 的 13C NMR 谱，并通过用重氮甲烷和 [13C] 重氮甲烷转化为已知的伐拉辛 N-三氟乙酰胺，独立指定了结构。化合物 4 是手性的，并且由于苯并五硫杂环的反转受限而表现出不寻常的立体异构现象。 Lissoclinotoxin A (4) 和 D (6) 对白色念珠菌表现出抗真菌活性。自从 Schmitzand 同事于 1983 年发现安非脒以来，*1 吡啶吖啶生物碱已作为一类来自海绵和海鞘的生物碱出现，具有显着的抗真菌、细胞毒性和 DNA 结合特性。研究表明，Dercitin、2、3 kuononiamine D、4、5 和 neoamphime-dine6 可以嵌入 DNA，而 neoamphi-medine（而非 dercitin）抑制拓扑异构酶 II。 6 Kuanoniamine D5 和 2-bromoeptoclinidone7 以高结合常数螯合过渡金属离子，这一特性可能在其细胞毒性作用中发挥作用。 Meridine 是从海鞘 Am-phicarpa meridiana8 和海绵 Corticum sp. 9 中独立分离出来的，对白色念珠菌具有显着的抗真菌活性，这一特性与抑制核酸合成有关。 9 抗肿瘤四环生物碱 Varamine A 和 B10 以及 diplamine11 是一组不太常见的含硫吡啶吖啶类化合物的例子。/3-咔啉和四氢-/3-咔啉，包括从几种热带海鞘中分离出来的 eudistomins12，已显示出抗肿瘤和抗病毒活性。在本报告中，我们证明了来自三个不同生物合成途径的次级代谢
Five new alkaloids, lissoclin A (1), lissoclin B (2), lissoclin C (3), lissoclinotoxin C (5), and the dimeric lissoclinotoxin D (6), were isolated along with the known compounds lissoclinotoxin A (4), 2-phenylethylamine (11), and 6-bromotryptamine (12) from Lissoclinum sp. collected from the Great Barrier Reef, Australia. Lissoclin A (1) undergoes photorearrangement to a new benzo-1, 3-oxathiazoline 10. The 13C NMR spectrum of 4 is reported for the first time and the structure independently assigned by conversion to the known varacin N-trifluoroacetamide with diazomethane and [13C] diazomethane. Compound 4 is chiral and exhibits unusual stereoisomerism due to restricted inversion about the benzopentathiepin ring. Lissoclinotoxin A (4) and D (6) exhibit antifungal activity against Candida albicans.Since the discovery of amphimedine by Schmitzand co-workers in 1983,* 1 pyridoacridine alkaloids have emerged as a class of alkaloids from sponges and ascidians with significant antifungal, cytotoxic, and DNA binding properties. Dercitin, 2, 3 kuononiamine D, 4, 5 and neoamphime-dine6 were shown to intercalate DNA while neoamphi-medine, but not dercitin, inhibits topoisomerase II. 6 Kuanoniamine D5 and 2-bromoleptoclinidone7 chelate transition metal ions with high binding constants, a property that may play a role in their cytotoxic effects. Meridine, isolated independently from the ascidian Am-phicarpa meridiana8and sponge Corticum sp., 9 displays significant antifungal activity against Candida albicans, a property that is related to inhibition of nucleic acid synthesis. 9 The antineoplastic tetracyclic alkaloids varamine A and B10 and diplamine11 are examples of a less common group of sulfur-containing pyridoacridines./3-Carbolines and tetrahydro-/3-carbolines, including the eudistomins12 isolatedfrom several species of tropical ascidians, have shown activity as antitumor and antiviral agents. In this report, we demonstrate secondary me-tabolism from three distinct biosynthetic pathways within