Mucocin: A New Annonaceous Acetogenin Bearing a Tetrahydropyran Ring
Mucocin: A New Annonaceous Acetogenin Bearing a Tetrahydropyran Ring
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Mucocin：一种带有四氢吡喃环的新番荔枝苷元
DOI：
10.1021/ja00146a037
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发表时间：
1995
影响因子：
15
通讯作者：
J. McLaughlin
中科院分区：
文献类型：
--
作者：
G. Shi;D. Alfonso;M. Fatope;L. Zeng;Z. Gu;Geng;K. He;J. MacDougal;J. McLaughlin
基于它们作为新的抗肿瘤药物的潜在潜力，1我们对卷柏属植物的活性叶进行了研究。番荔枝科(Baill.)其他地方也报道了一些初步结果。2在此，我们报道了粘蛋白的分离、绝对结构测定和生物活性(图1)。以前已知的乙酰生素的特征通常是它们带有一到三个四氢呋喃(THF)环。11是报道的第一个含羟基四氢吡喃(THP)环和四氢吡喃(THF)环的番荔枝内酯。这一发现为番荔枝内酯家族增加了一种新的骨骼类型。1的分离采用盐虾致死试验(BST)3 45，采用重复开放色谱柱和高效液相色谱分离乙醇提取物。2，4用高分辨原子吸收光谱确定1的分子式为CsvHeeOg(MH+，m/z=639.4828，标度为639.4836)。DEPT实验揭示了两个甲基、10个亚甲基和两个季碳的存在(一些亚甲基碳峰在<；529.5处重叠)。平面结构是通过COSY、EIMS和其TMS衍生物的EIMS建立的(图1)。在1的双中继COSY谱中成功地观察到了对应于H-20/23的交叉峰。通过与已知番荔枝内酯的~(13)C核磁共振数据(表1)的比较，证实了甲基化的，/9-不饱和的4-羟基内酯的存在。1建立了1的相对立体化学结构。应用Bom规则，H-16在C-15/16上的<；3值为三种关系。通过与合成模型的~3C核磁共振数据(从C-12到C-16)的紧密匹配，提出了反式四氢呋喃环的构型归属
Motivated by their promising potential as new antitumor drugs, 1 we have now investigated the bioactive leaves of Rollinia mucosa (Jacq.) Baill.(Annonaceae). Some initial results have been reported elsewhere. 2 Herein, we report the isolation, absolute structure determination, and bioactivity of mucocin (1, Figure 1). The previously known acetogenins are usually characterized (among other features) by their bearing one to three tetrahydrofuran (THF) rings. 1 1 is the first annonaceous acetogenin to be reported that bears a hydroxylated tetrahydropyran (THP) ring along with a THF ring. This finding adds a new skeletal type to the family of annonaceous acetogenins. The isolation of 1 was guided by the brine shrimp lethality test (BST) 3 45using repetitive open column and HPLC chromatography to separate the partitioned ethanol extract. 2, 4 The molecular formula of 1 was determined as CsvHeeOg by HRFABMS (MH+, m/z found 639.4828, caled 639.4836). A DEPT experiment revealedthe presence of two methyl, 10 methine, and two quaternary carbons (some methylene carbon peaks overlapped at< 5 29.5). The planar structure was estab-lished by means of COSY, EIMS, and EIMS of its TMS derivative (la, Figure 1). The cross peak corresponding to H-20/23 was successfully observed in the double-relayed COSY spectrum of 1. The existence of the methylated,/9-unsaturated y-lactone with a 4-OH was confirmed by comparing the and 13C NMR data (Table 1) with those of known annonaceous acetogenins. 1The relative stereochemistry of 1 was established as follows. Applying Bom’s rule, 5 the< 3 value of H-16 indicated a three relationship at C-15/16. The configurational assignment of the THF ring as trans was suggested by the close match of the, 3C NMR data (from C-12to C-16) with those of synthetic model