(Z)-2,3,7-trimethylocta-2,6-dien-1-ol | 1025394-27-7

• 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: (Z)-2,3,7-trimethylocta-2,6-dien-1-ol
• 英文别名: (2Z)-2,3,7-trimethylocta-2,6-dien-1-ol
• CAS: 1025394-27-7
• 化学式: C₁₁H₂₀O
• 分子量: 168.279
• InChiKey: QVCKBQDDEUWNIT-KHPPLWFESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  (Z)-2,3,7-trimethylocta-2,6-dien-1-ol 在 对甲苯磺酸 作用下， 以 硝基甲烷 为溶剂， 反应 1.0h， 以22%的产率得到2-Methyl-α-terpineol
  参考文献：
  名称：

  Incubation of 2-methylisoborneol synthase with the intermediate analog 2-methylneryl diphosphate

  摘要：

  将合成的 2-甲基麦角酰二磷酸酯（2-MeNPP，10）与 2-甲基异龙脑合成酶（MIBS）孵育，得到的混合物产物与天然底物（E）-2-甲基麦角酰二磷酸酯（3，2-MeGPP）得到的产物有很大不同。经手性 GCâMS 分析测定，(-)-2-甲基异龙脑（1）的比例从 89% 降至 17%，而 2-亚甲基龙脑烯（4）的比例从 10% 增至 26%，同分异构体 2-甲基-2-龙脑烯（5）和 1-甲基莰烯（6）的相对产率基本保持不变（均小于 1%）。由 MIBS 催化环化 2-MeNPP (10) 得到的大部分产物混合物由反常的单环同单萜 (±)-2-methylllimonene (15, 39%) 和 2-methyl-α-terpineol (13, 10%) 以及酰基衍生物 2-methylnerol (11, 7%) 和 2-methyllinalool (14, <1%)组成。使用[1-3H]-2-甲基内酰二磷酸（2-MeNPP）测定的MIBS催化反应的稳态动力学参数为：kcat 0.0046±0.0003âsâ1，Km 18±6âμm，kcat/Km 2.55 à 102 Mâ1âsâ1。相比之下，天然底物2-MeGPP的kcat为0.105±0.007âsâ1，Km为95±49âμm，kcat/Km为1.11 à 103 Mâ1âsâ1。结合早先对MIBS的X射线晶体学研究，以及之前对与之有机械相关性的植物单萜烯环化酶--二磷酸冰片酯合成酶的研究，这些结果为了解原生底物和中间体及其类似物的结合和环化提供了重要的启示。

  DOI：

  10.1038/ja.2017.24
• 作为产物：
  描述：

  (Z)-2,3,7-trimethylocta-2,6-dienoic acid ethyl ester 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 15.0h， 以64%的产率得到(Z)-2,3,7-trimethylocta-2,6-dien-1-ol
  参考文献：
  名称：

  粘液细菌Nanonocystis exedens对异味2-甲基异冰片醇的生物合成。

  摘要：

  DOI：

  10.1002/anie.200702496

文献信息

• S _N 2 Reactions at Tertiary Carbon Centers in Epoxides
  作者：Yong‐Qiang Zhang、Christina Poppel、Anastasia Panfilova、Fabian Bohle、Stefan Grimme、Andreas Gansäuer

  DOI：10.1002/anie.201702882

  日期：2017.8.7

  Described herein is a novel concept for SN2 reactions at tertiary carbon centers in epoxides without activation of the leaving group. Quantum chemical calculations show why SN2 reactions at tertiary carbon centers are proceeding in these systems. The reaction allows flexible synthesis of 1,3‐diol building blocks for natural product synthesis with excellent control of the relative and absolute configurations

  本文描述了在环氧化物中叔碳中心处的S N 2反应而不活化离去基团的新颖概念。量子化学计算表明为什么在这些系统中三级碳中心的S N 2反应正在进行。该反应可以灵活地合成1,3-二醇结构单元，用于天然产物的合成，并具有相对和绝对构型的出色控制。
• Biochemistry and Molecular Genetics of the Biosynthesis of the Earthy Odorant Methylisoborneol in <i>Streptomyces coelicolor</i>
  作者：Chieh-Mei Wang、David E. Cane

  DOI：10.1021/ja803639g

  日期：2008.7.1

  Methylisoborneol (2) is a volatile organic compound produced by a wide variety of Actinomycetes soil orgainisms, myxobacteria, and cyanobacteria. It has an unusually low odor threshold and, together with geosmin, is responsible for the characteristics smell of moist soil as well as unpleasant taste and odor episodes assoiciated with public water supplies and contamination of various foodstuffs, including fish, wine and beer. Despite considerable interest in detection and remediation of methylisoborneal, the biosynthesis of this methylated monoterpene has been obscure. In Streptomyces coelicor, the sco7700 and sco7701 genes are shown to correspond to a two-gene operon responsible for methylisoborneol biosynthesis. Both genes have been amplified by PCR and the resulting DNA has been cloned and expressed in Escherichia coli. Incubation of recombinant SCO7701 protein, annotated as a possible C-methyltransferase, with geranyl diphosphate (1) and S-adenosylmethionine gave the previously unknown compound. (E)-2-methylgeranyl diphosphate (3). Incubation of 3 in the presence of Mg2+ with recombinant SCO7700, previously annotated only as a possible metal-binding protein or terpenoid synthase, resulted in the formation of 2-methylisoborneal (2). The steady-state kinetic parameters for both biochemical reactions have been determined. Incubation of geranyl diphosphate and S-adenosylmethionine with a mixture of both SCO7700 and SCO7701 resulted in formation of methylisoborneal (2). Cyclization of 2-methylgeranyl diphosphate (3) to methylisoborneal (2) likely involves the intermediacy of 2-methylinalyl diphosphate.