Alfred-Wegener-Institut für Polar- und Meeresforschung in der Helmholtz-Gemeinschaft, Am Handelshafen 12, D-27570 Bremerhaven, Germany.
J Nat Prod. 2012 Feb 24;75(2):127-30. doi: 10.1021/np200514g. Epub 2012 Feb 14.
The structure elucidation of the palau'amine congener tetrabromostyloguanidine (1), which used interproton distances from ROESY spectra as restraints in a computational approach, the so-called fc-rDG/DDD method, led to a revision of the relative configuration of palau'amine (2) and its congeners in 2007. The recent total synthesis of (±)-palau'amine (2) subsequently confirmed the computed structural revision of the relative configuration. In order to test a broader application range of the fc-rDG/DDD method, the present study investigated two additional dimeric pyrrole-imidazole alkaloids, axinellamine A (3) and 3,7-epi-massadine chloride (4). These calculations allowed the simultaneous assignment of the relative configuration for all eight stereogenic centers of compounds 3 and 4 without using any information from the reported configurations. In contrast to the palau'amine congeners, the fc-rDG/DDD method confirmed the relative configuration originally described for axinellamine A (3) and 3,7-epi-massadine chloride (4).
结构阐明了 palau'amine 同系物 tetrabromostyloguanidine（1），该化合物使用 ROESY 光谱中的质子间距离作为计算方法（所谓的 fc-rDG/DDD 方法）中的约束条件，从而对 palau'amine（2）及其同系物的相对构型进行了修订。最近（±）-palau'amine（2）的全合成随后证实了相对构型的计算结构修订。为了测试 fc-rDG/DDD 方法的更广泛应用范围，本研究还研究了另外两种二聚吡咯-咪唑生物碱，axinellamine A（3）和 3,7-epi-massadine 氯化物（4）。这些计算允许同时分配化合物 3 和 4 中所有八个立体中心的相对构型，而无需使用任何报告构型的信息。与 palau'amine 同系物不同，fc-rDG/DDD 方法证实了最初描述的 axinellamine A（3）和 3,7-epi-massadine 氯化物（4）的相对构型。
