Rufomycins or Ilamycins: Naming Clarifications and Definitive Structural Assignments.
Rufomycins or Ilamycins: Naming Clarifications and Definitive Structural Assignments.
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DOI：
10.1021/acs.jnatprod.1c00198
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发表时间：
2021-10-22
影响因子：
5.1
通讯作者：
McAlpine JB
中科院分区：
文献类型：
--
作者：
Zhou B;Achanta PS;Shetye G;Chen SN;Lee H;Jin YY;Cheng J;Lee MJ;Suh JW;Cho S;Franzblau SG;Pauli GF;McAlpine JB
卢福霉素和伊拉霉素是同一类环肽的同义词，目前包含 33 种结构特征分离物和 9 种半合成衍生物。新结构的阐明优先考虑名称的整合，并建立了四种非对映异构体红霉素与 2-哌啶酮的结构，命名为红霉素 4-7，包括完整的 1H/13C NMR 归属。 CH-5（氨基酸 #5 中的半缩醛胺碳）的特征 HSQC 交叉峰允许在该环内指定立体中心 C-4 和 C-5。由红霉素 4 和 6 混合物制备半合成衍生物（红霉素 SS 1、2 和 3），以验证结构分配。基于rufomycins 2和4的X射线晶体结构，考虑到rufomycins 7 vs 4-6与rufomycinSS 1 vs 2和3相比的NMR差异，并考虑到rufomycinSS 2和3中都存在两种主要构象异构体A和B，进行了结构建模。总的来说，本文讨论了立体异构体及其可能的 3D 构象异构体的 NMR 光谱差异，并将这些差异与抗结核分枝杆菌活性相关联。此外，回顾历史可以优先考虑这组抗生素的名称和编号方案，并为所有当前已知的成员、天然和半合成衍生物提供统一的命名法，并有助于适应未来的发现。
Rufomycin and ilamycin are synonymous for the same class of cyclopeptides, currently encompassing 33 structurally characterized isolates and 9 semisynthetic derivatives. Elucidation of new structures prioritized the consolidation of the names and established the structures of four diastereoisomeric rufomycins with a 2-piperidinone, named rufomycins 4–7, including full 1H/13C NMR assignments. The characteristic HSQC cross-peak for the CH-5, the hemiaminal carbon in amino acid #5, allows assignment of the stereocenters C-4 and C-5 within this ring. Semisynthetic derivatives (rufomycinSS 1, 2, and 3) were prepared from a rufomycins 4 and 6 mixture to validate the structural assignments. Based on the X-ray crystal structures of rufomycins 2 and 4, considering the NMR differences of rufomycins 7 vs 4–6 compared to rufomycinSS 1 vs 2 and 3, and taking into account that two major conformers, A and B, occur in both rufomycinSS 2 and 3, structural modeling was pursued. Collectively, this paper discusses the NMR spectroscopic differences of the stereoisomers and their possible 3D conformers and correlates these with the anti-Mycobacterium tuberculosis activity. In addition, a look at the history prioritizes names and numbering schemes for this group of antibiotics and leads to consolidated nomenclature for all currently known members, natural and semisynthetic derivatives, and serves to accommodate future discoveries.
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影响因子：
3.3
作者：
HOCHLOWSKI, JE;SWANSON, SJ;MCALPINE, JB
通讯作者：
MCALPINE, JB
具有不寻常结构单元的伊拉霉素生物合成和增强抗结核药物的工程化生产
影响因子：
16.6
作者：
Ma J;Huang H;Xie Y;Liu Z;Zhao J;Zhang C;Jia Y;Zhang Y;Zhang H;Zhang T;Ju J
通讯作者：
Ju J
影响因子：
3.5
作者：
CARY, LW;TAKITA, T;OHNISHI, M
通讯作者：
OHNISHI, M
影响因子：
3.6
作者：
Choules, Mary P.;Klein, Larry L.;Pauli, Guido F.
通讯作者：
Pauli, Guido F.
影响因子：
15
作者：
IWASAKI, H;WITKOP, B
通讯作者：
WITKOP, B