Disproof of the Proposed Structures of Bradyoxetin, a Putative Bradyrhizobium japonicum Signaling Molecule, and HMCP, a Putative Ralstonia solanacearum Quorum-Sensing Molecule
Disproof of the Proposed Structures of Bradyoxetin, a Putative Bradyrhizobium japonicum Signaling Molecule, and HMCP, a Putative Ralstonia solanacearum Quorum-Sensing Molecule
复制标题
反驳缓生素（一种假定的日本慢生根瘤菌信号分子）和 HMCP（一种假定的青枯菌群体感应分子）的拟议结构
DOI：
10.1021/acs.jnatprod.0c01369
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发表时间：
2021
影响因子：
5.1
通讯作者：
Kai Kenji
中科院分区：
文献类型：
--
作者：
Yajima Arata;Katsuta Ryo;Shimura Mikaho;Yoshihara Ayaka;Saito Tatsuo;Ishigami Ken;Kai Kenji
首先，我们重新审视了慢生根瘤菌（Bradyrhizobium japonicum）的一个假定的细胞密度因子慢生根瘤菌（Bradyrhizobium japonicum）的NMR数据，发现了一些不一致的结构。为了阐明正确的结构，我们合成了模型氧杂环丁烷化合物，并证实合成化合物的NMR数据不匹配的报道。在重新解释所报道的NMR数据后，我们得出结论，缓激肽必须是氯霉素。接下来，合成了一些2-羟基-4-（（甲氨基）（苯基）甲基）环戊酮（HMCP）的衍生物，HMCP是青枯雷尔氏菌的推定群体感应分子。所合成化合物的核磁共振谱与已报道的天然产物完全不同。在理论研究的基础上，采用密度泛函理论计算了1H和13 C NMR化学位移，证实了所合成化合物结构的正确性。这些结果强烈表明HMCP的拟议结构可能是不正确的。
First, we revisited the reported NMR data of bradyoxetin, a putative cell density factor ofBradyrhizobium japonicum, and found some inconsistencies in the proposed structure. To elucidate the correct structure, we synthesized model oxetane compounds and confirmed that the NMR data of the synthetic compounds did not match those of the reported bradyoxetin. After reinterpreting the reported NMR data, we concluded that bradyoxetin must be chloramphenicol. Next, some derivatives of 2-hydroxy-4-((methylamino)(phenyl)methyl)cyclopentanone (HMCP), which is a putative quorum-sensing molecule ofRalstonia solanacearum, were synthesized. The NMR spectra of the synthesized compounds were completely different from those of the reported natural products. Based on theoretical studies, including the estimation of1H and13C NMR chemical shifts using density functional theory calculations, we confirmed the correctness of the structure of the synthesized compound. These results strongly suggest that the proposed structure of HMCP could be incorrect.