Structural assignment of tetrabromostyloguanidine:: Does the relative configuration of the palau'amines need revision?
Structural assignment of tetrabromostyloguanidine:: Does the relative configuration of the palau'amines need revision?
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DOI：
10.1002/anie.200604076
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发表时间：
2007-01-01
影响因子：
16.6
通讯作者：
Koeck, Matthias
中科院分区：
文献类型：
--
作者：
Grube, Achim;Koeck, Matthias
帕劳胺及其同系物的全合成是当前有机合成化学的一个重要课题。[1]到目前为止，没有一个参与合成的研究小组能够获得palauamine的完整结构。在此，我们提出了一个新的同系物帕劳胺，四溴styloguanidine（1;方案1），这是从海洋海绵Stylissa caribica分离。与已发表的帕劳胺同系物的相对构型相反，我们对1的研究揭示了不同的相对构型。二溴帕劳胺（2c）也是从同一种海绵中分离出来的。Axinellidae和Dictyonellidae的海绵是研究最多的海洋无脊椎动物之一，[2]许多次级代谢产物已经从这些海绵中分离出来并报道，特别是吡咯-咪唑生物碱。这个生物碱家族中大约有100个成员与奥洛依丁生物合成相关。[3，4]利用质谱引导分离技术对海洋海绵Stylissa caribica [5]进行了研究，得到了几种新的吡咯-咪唑生物碱：4-溴吡咯-2-羧基-N（ε）-赖氨酸，[6] 4-溴吡咯-2-羧基精氨酸，[6]氧代环stylidol，[7]以及stylissestrin A和B。[8]在这项研究的过程中，一个化合物与以前未观察到的质量和Br 4Cl同位素模式被检测到。我们报道了这个新化合物1的分离和结构鉴定，特别关注氮杂双环[3.3]的相对构型。0]辛烷核（方案1）。
The total synthesis of palau amine and its congeners is currently a major topic in synthetic organic chemistry.[1] So far, none of the research groups involved in the syntheses have managed to reach the complete structure of palauamine. Herein, we present a new congener of palau amine, tetrabromostyloguanidine (1; Scheme 1) which was isolated from the marine sponge Stylissa caribica. In contrast to the relative configuration of the palau amine congeners that have been published, our studies on 1 have revealed a different relative configuration. Dibromopalau amine (2c) was also isolated from the same sponge.Sponges of the families Axinellidae and Dictyonellidae are among the most investigated marine invertebrates,[2] with many secondary metabolites having been isolated and reported from these sponges, especially pyrrole-imidazole alkaloids. Approximately 100 members of this alkaloid family are biosynthetically related to oroidin.[3, 4] The marine sponge Stylissa caribica [5] was studied by using MS-guided fractionation to afford several new pyrrole-imidazole alkaloids: 4-bromopyrrole-2-carboxy-N (ε)-lysine,[6] 4-bromopyrrole-2-carboxyarginine,[6] oxocyclostylidol,[7] and the stylissadines A and B.[8] In the course of this study, a compound with a previously unobserved mass and with a Br4Cl isotopic pattern was detected. We report the isolation and structure elucidation of this new compound 1, with a particular focus on the relative configuration of the azabicyclo [3.3. 0] octane core (Scheme 1).