methyl pseudomonate A

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl pseudomonate A
• 英文别名: mupirocin methyl ester；methyl 9-[(E)-4-[(2S,3R,4R,5S)-3,4-dihydroxy-5-[[(2S,3S)-3-[(2S,3S)-3-hydroxybutan-2-yl]oxiran-2-yl]methyl]oxan-2-yl]-3-methylbut-2-enoyl]oxynonanoate
• 化学式: C₂₇H₄₆O₉
• 分子量: 514.657
• InChiKey: CJKAHSOGVKAYJX-KPPUQUFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  36
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  135
• 氢给体数：
  3
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl pseudomonate A 生成 <(2S,3R,4R,5S)-5-<(2S,3S,4S,5S)-(2,3-epoxy-5-hydroxy-4-methylhexyl)>-3,4-dihydroxytetrahydropyran-2-yl>acetone
  参考文献：
  名称：

  LUK, K.;CLAYTON, J. P.;ROGERS, N. H.

  摘要：

  DOI：
• 作为产物：
  描述：

  莫匹罗星 生成 methyl pseudomonate A
  参考文献：
  名称：

  pseudo酸C的结构和构型

  摘要：

  从荧光假单胞菌菌株的发酵物中分离出了一种新的抗生素假单胞酸C（2a），该菌株产生了已知且结构相似的抗生素假单胞酸A（1a）和B（1c）。

  DOI：

  10.1016/s0040-4039(00)71533-4

文献信息

• Site-selective oxidation, amination and epimerization reactions of complex polyols enabled by transfer hydrogenation
  作者：Christopher K. Hill、John F. Hartwig

  DOI：10.1038/nchem.2835

  日期：2017.12

  for selective reactions of complex polyol structures. We present a new ruthenium catalyst with a unique efficacy for the selective oxidation of a single hydroxyl group among many in unprotected polyol natural products. This oxidation enables the introduction of nitrogen-based functional groups into such structures that lack nitrogen atoms and enables a selective alcohol epimerization by stepwise or

  带有一个或多个羟基的多氧化碳氢化合物包含大量天然和合成化合物，通常具有强大的生物活性。在合成化学中，醇是羰基的重要前体，然后可以将其转化为多种基于氧或氮的官能团。因此，将天然产物中的单个羟基选择性转化为酮将能够选择性引入非天然官能团。然而，已知的将简单的醇或什至在包含多个受保护的官能团的分子中的醇转化的方法不适用于复杂的多元醇结构的选择性反应。我们提出了一种新型的钌催化剂，该催化剂具有独特的功效，可以选择性氧化多个未保护的多元醇天然产物中的单个羟基。该氧化使得能够将氮基官能团引入缺乏氮原子的这种结构中，并能够通过逐步或可逆的氧化和还原来进行选择性醇差向异构化。
• Catalyst recognition of cis-1,2-diols enables site-selective functionalization of complex molecules
  作者：Xixi Sun、Hyelee Lee、Sunggi Lee、Kian L. Tan

  DOI：10.1038/nchem.1726

  日期：2013.9

  Carbohydrates and natural products serve essential roles in nature, and also provide core scaffolds for pharmaceutical agents and vaccines. However, the inherent complexity of these molecules imposes significant synthetic hurdles for their selective functionalization and derivatization. Nature has, in part, addressed these issues by employing enzymes that are able to orient and activate substrates within a chiral pocket, which increases dramatically both the rate and selectivity of organic transformations. In this article we show that similar proximity effects can be utilized in the context of synthetic catalysts to achieve general and predictable site-selective functionalization of complex molecules. Unlike enzymes, our catalysts apply a single reversible covalent bond to recognize and bind to specific functional group displays within substrates. By combining this unique binding selectivity and asymmetric catalysis, we are able to modify the less reactive axial positions within monosaccharides and natural products. The manipulation of complex molecules offers an avenue for developing new therapeutics and biological probes. Here, a catalyst is described that forms a covalent bond to the substrate before selectively functionalizing a proximal functional group. Cis-1,2-diols are targeted allowing for the derivatization of the axial hydroxyls of monosaccharides in the presence of unprotected equatorial hydroxyls.

  碳水化合物和天然产物在自然界中扮演着重要角色，并为制药剂和疫苗提供了核心骨架。然而，这些分子的固有复杂性给其选择性功能化和衍生化带来了重大的合成挑战。自然界在一定程度上通过利用酶来解决这些问题，这些酶能够在手性口袋中定向和激活底物，从而显著提高有机转化的速率和选择性。本文展示了，在合成催化剂的情境下，类似的接近效应也可以被利用来实现复杂分子的一般性和可预测的位点选择性功能化。与酶不同，我们的催化剂采用单一的可逆共价键来识别和结合底物中的特定功能基团。通过结合这种独特的结合选择性和不对称催化，我们能够修饰单糖和天然产品中较不活跃的轴向位置。复杂分子的操作为开发新的治疗药物和生物探针提供了途径。这里描述了一种催化剂，它在与底物形成共价键后，选择性地功能化邻近的功能基团。目标为顺-1,2-二醇，允许在未保护的赤道羟基存在下衍生化单糖的轴向羟基。
• Experimental and Computational Studies on Regiodivergent Chiral Phosphoric Acid Catalyzed Cycloisomerization of Mupirocin Methyl Ester
  作者：Sibin Wang、Alonso J. Arguelles、Jia‐Hui Tay、Miyuki Hotta、Paul M. Zimmerman、Pavel Nagorny

  DOI：10.1002/chem.201905222

  日期：2020.4.6

  This article presents a new strategy for achieving regiocontrol over the endo versus exo modes of cycloisomerizations of epoxide-containing alcohols, which leads to the formation of five- or six-membered cyclic ethers. Unlike traditional methods relying on achiral reagents or enzymes, this approach utilizes chiral phosphoric acids to catalyze the regiodivergent selective formations of either tetrahydrofuran-

  本文提出了一种新策略，用于实现对含环氧化物醇环异构化的内型与外型模式的区域控制，从而形成五元或六元环醚。与依赖非手性试剂或酶的传统方法不同，该方法利用手性磷酸来催化区域差异选择性形成含有四氢呋喃或四氢吡喃的产物。通过使用含环氧化物的抗生素莫匹罗星甲酯作为底物，证明催化手性磷酸(R)-TCYP和(S)-TIPSY可用于实现六元内切产物( 95:5 rr) 或五元 exo 产物 (77:23 rr)，相应地。发现这种环化在涉及各种非手性酸、碱或缓冲液的标准条件下是非选择性的。随后使用最先进的量子化学溶液进行的机理研究提供了势能表面的描述，这与实验观察完全一致。基于这些结果，获得了非常详细的反应路径，并提出了用于外型和内型产物形成的协调且高度同步的机制。
• The chemistry of pseudomonic acid. Part 4. αβ-Unsaturated ketones derived from monic acid A and its derivatives
  作者：Steven Coulton、Peter J. O'Hanlon、Norman H. Rogers

  DOI：10.1039/p19820000729

  日期：——

  Routes to the preparation of αβ-unsaturated ketones (1k–m) have been investigated. n-Butylmanganese(II) chloride was particularly useful for preparing the ketones (1m) from the readily available monic acid A (1b), the nucleus of pseudomonic acid A (1a).

  已经研究了制备αβ-不饱和酮（1k–m）的途径。氯化正丁基锰（II）特别适用于从容易获得的单酸A（1a）的核A（1b）中制备酮（1m）。
• Mupirocin F: structure elucidation, synthesis and rearrangements
  作者：Robert W. Scott、Annabel C. Murphy、Ji’en Wu、Joanne Hothersall、Russell J. Cox、Thomas J. Simpson、Christopher M. Thomas、Christine L. Willis

  DOI：10.1016/j.tet.2011.05.021

  日期：2011.7

  The structures of two novel metabolites, mupirocins F and F2, from extracts of the mupF mutant of Pseudomonas fluorescens were elucidated by spectroscopic methods. Methyl mupirocin F was synthesised from the triol methyl pseudomonate A by selective oxidation of the 7-hydroxyl group thus firmly establishing the structure of the natural product. Rearrangement of the densely functionalised skeleton led to unusual bicyclic and tricyclic products. (C) 2011 Elsevier Ltd. All rights reserved.