(+)-T-muurolol

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+)-T-muurolol
• 英文别名: ent-T-muurolol；(+)-torreyol；α-muurolol；δ-cadinol；(+)-tau-Muurolol；(1R,4R,4aS,8aR)-1,6-dimethyl-4-propan-2-yl-3,4,4a,7,8,8a-hexahydro-2H-naphthalen-1-ol
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: LHYHMMRYTDARSZ-KBUPBQIOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+)-T-muurolol 在 cytochrome P₄₅₀ monooxygenase CYP₂₆₇B₁ from Sorangium cellulosum 作用下， 生成 、 、 (1S,6R,7R,10R)-7α-hydroxy-4-oxo-(+)-α-muurolene
  参考文献：
  名称：

  研究萜烯的细胞色素P450氧化的同位素标记策略。

  摘要：

  将来自Sorangium cellulosum的细胞色素P450单加氧酶CYP267B1用于倍半萜烯醇T-muurolol和isodauc-8-en-11-ol的酶促氧化。各种同位素标记的香叶基和法呢基二磷酸酯用于微量反应中的产物鉴定，确定未知化合物的绝对构型，遵循细胞色素P450催化的羟基化步骤的立体化学过程，并研究动力学同位素效应。总的来说，这项研究表明，同位素标记的萜烯前体对于跟踪细胞色素P450依赖的萜烯氧化非常有用。

  DOI：

  10.1002/cbic.201800215
• 作为产物：
  描述：

  farnesyl pyrophosphate 在 (+)-T-muurolol synthase from Roseiflexus castenholzii 、 碳酸氢铵 作用下， 以 aq. buffer 为溶剂， 反应 4.0h， 生成 (+)-T-muurolol
  参考文献：
  名称：

  倍半萜和双萜的EI-MS裂解机理

  摘要：

  通过使用每个分子的全部15或20种酶促合成的13 C 1标记的同位素异构体，研究了一种细菌倍半萜烯醇和四种二萜烃的EI-MS断裂机理。特定位置的质量偏移分析表明形成每个碎片离子的碳主链部分。HR-MS / MS分析已开发出可能的破碎机制，并进一步加强了这种破碎机制。

  DOI：

  10.1002/ejoc.201800217

文献信息

• Lessons from 1,3-Hydride Shifts in Sesquiterpene Cyclizations
  作者：Jan Rinkel、Patrick Rabe、Paolina Garbeva、Jeroen S. Dickschat

  DOI：10.1002/anie.201608042

  日期：2016.10.17

  initial 1,10‐cyclisation‐1,3‐hydride shift cascades. Enzymes with products of known absolute configuration showed a coherent stereochemical course, except for (−)‐α‐amorphene synthase, for which the obtained results are better explained by an initial 1,6‐cyclisation. The link between the absolute configuration of the product and the stereochemical course of the 1,3‐hydride shifts enabled assignment of

  用7种细菌倍半萜环化酶将立体标记的前体转化，以研究其最初的1,10-环化-1,3-氢化物移位级联反应的立体化学。带有已知绝对构型的产物的酶显示出连贯的立体化学过程，除了（-）-α-Amorphene合酶外，最初的1,6-环化可以更好地解释所获得的结果。产品的绝对构型与1,3-氢化物转变的立体化学过程之间的联系使得可以分配三种酶产物的绝对构型，这可以通过常见副产物胚芽戊二烯D-4-ol的绝对构型独立确认。
• Antimalarial Properties of Simplified Kalihinol Analogues
  作者：Mary Elisabeth Daub、Jacques Prudhomme、Choukri Ben Mamoun、Karine G. Le Roch、Christopher D. Vanderwal

  DOI：10.1021/acsmedchemlett.7b00013

  日期：2017.3.9

  Several kalihinol natural products, members of the broader isocyanoterpene family of antimalarial agents, are potent inhibitors of Plasmodium falciparum, the agent of the most severe form of human malaria. Our previous total synthesis of kalihinol B provided a blueprint to generate many analogues within this family, some as complex as the natural product and some much simplified and easier to access. Each analogue was tested for blood-stage antimalarial activity using both drug-sensitive and -resistant P. falciparum strains. Many considerably simpler analogues of the kalihinols retained potent activity, as did a compound with a different decalin scaffold made in only three steps from sclareolide. Finally, one representative compound showed reasonable stability toward microsomal metabolism, suggesting that the isonitrile functional group that is critical for activity is not an inherent liability in these compounds.
• Genome Mining in Streptomyces clavuligerus: Expression and Biochemical Characterization of Two New Cryptic Sesquiterpene Synthases
  作者：Yunfeng Hu、Wayne K.W. Chou、Russell Hopson、David E. Cane

  DOI：10.1016/j.chembiol.2010.11.008

  日期：2011.1

  Two presumptive terpene synthases of unknown biochemical function encoded by the sscg_02150 and sscg_03688 genes of Streptomyces clavuligerus ATCC 27074 were individually expressed in Escherichia coli as N-terminal-His(6)-tag proteins, using codon-optimized synthetic genes. Incubation of recombinant SSCG_02150 with farnesyl diphosphate (1, FPP) gave (-)-delta-cadinene (2) while recombinant SSCG_03688 converted FPP to (+)-T-muurolol (3). Individual incubations of (-)-delta-cadinene synthase with [1,1-H-2(2)]FPP (1a), (1S)-[1-H-2]-FPP (1b), and (1R)-[1-H-2]-FPP (1c) and NMR analysis of the resulting samples of deuterated (-)-delta-cadinene supported a cyclization mechanism involving the intermediacy of nerolidyl diphosphate (4) leading to a helminthogermacradienyl cation 5. Following a 1,3-hydride shift of the original H-1(si) of FPP, cyclization and deprotonation will give (-)-delta-cadinene. Similar incubations with recombinant SSCG_03688 supported an analogous mechanism for the formation of (+)-T-muurolol (3), also involving a 1,3-hydride shift of the original H-1(si) of FPP.
• Bowden, Bruce F.; Coll, John C.; Willis, Richard H., Australian Journal of Chemistry, 1986, vol. 39, # 10, p. 1717 - 1722
  作者：Bowden, Bruce F.、Coll, John C.、Willis, Richard H.

  DOI：——

  日期：——
• The EI‐MS Fragmentation Mechanisms of Bacterial Sesquiterpenes and Diterpenes
  作者：Jan Rinkel、Patrick Rabe、Jeroen S. Dickschat

  DOI：10.1002/ejoc.201800217

  日期：2019.1.23

  The EI‐MS fragmentation mechanisms of one bacterial sesquiterpene alcohol and four diterpene hydrocarbons have been investigated by using all 15 or 20 enzymatically synthesised 13C1‐labelled isotopomers of each molecule. A position‐specific mass shift analysis indicated the parts of the carbon backbone that form each fragment ion. Plausible fragmentation mechanisms have been developed and further strengthened

  通过使用每个分子的全部15或20种酶促合成的13 C 1标记的同位素异构体，研究了一种细菌倍半萜烯醇和四种二萜烃的EI-MS断裂机理。特定位置的质量偏移分析表明形成每个碎片离子的碳主链部分。HR-MS / MS分析已开发出可能的破碎机制，并进一步加强了这种破碎机制。

表征谱图