(3S,7S)-3,7-dimethyl-1-tetradecanol | 1443233-06-4

• 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: (3S,7S)-3,7-dimethyl-1-tetradecanol
• 英文别名: (3S,7S)-3,7-dimethyltetradecan-1-ol
• CAS: 1443233-06-4
• 化学式: C₁₆H₃₄O
• 分子量: 242.445
• InChiKey: ZOSCFDIMEDGEMN-HOTGVXAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  17
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  (3S,7S)-3,7-dimethyl-1-tetradecanol 在 palladium 10% on activated carbon 、 氢气 、 氧气 、 copper(II) sulfate 、 间氯过氧苯甲酸 、 三苯基膦 、 lithium hexamethyldisilazane 、 肼 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 16.0h， 生成 (4S,8S,12S,16S,20S)-4,8,12,16,20-pentamethyl-1-heptacosanol
  参考文献：
  名称：

  Highly Stereocontrolled Total Synthesis of β-d-Mannosyl Phosphomycoketide: A Natural Product from Mycobacterium tuberculosis

  摘要：

  beta-D-Mannosyl phosphomycoketide (C-32-MPM), a naturally occurring glycolipid found in the cell walls of Mycobacterium tuberculosis, acts as a potent antigen to activate T-cells upon presentation by CD1c protein. The lipid portion of C-32-MPM contains, a C-32-mycoketide, consisting of a saturated oligoisoprenoid chain with five chiral methyl branches. Here we develop several stereocontrolled approaches to assemble the oligoisoprenoid chain with high stereopurity (>96%) using Julia-Kocienski olefinations followed by diimide reduction. By careful choice of olefination sites, we could derive all chirality from a single commercial compound, methyl (2S)-3-hydroxy-2-methylpropionate (>99% ee). Our approach is the first highly stereocontrolled method to prepare C-32-MPM molecule with >96% stereopurity from a single >99% ee starting material. We anticipate that our methods will facilitate the highly stereocontrolled synthesis of a variety of other natural products containing chiral oligoisoprenoid-like chains, including vitamins, phytol, insect pheromones, and archaeal lipids.

  DOI：

  10.1021/jo4006602
• 作为产物：
  描述：

  1-壬烷醇,2-甲基-,(S)- 在 四丁基氟化铵 、 (2-methylpropyl)lithium 、 戴斯-马丁氧化剂 、 copper(II) sulfate 、 9-硼双环[3.3.1]壬烷 、 间氯过氧苯甲酸 、 三苯基膦 、 lithium hexamethyldisilazane 、 肼 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 环己烷 为溶剂， 反应 19.5h， 生成 (3S,7S)-3,7-dimethyl-1-tetradecanol
  参考文献：
  名称：

  stereopure无环1,5- dimethylalkane chirons的合成：的高度甲基支化的天然产物积木

  摘要：

  朝stereopure一种有效的合成方法无环从甲基（2- 1,5- dimethylalkane积木- [R）-3-羟基-2-甲基丙酸酯（[R ）- 1（> 99％ee）和甲基（2-小号）-3-羟基2-甲基丙酸酯（小号） - 1（> 99％ee）的通过一系列的化学转化，包括朱莉娅- Kocienski烯和二酰亚胺还原的，被描述。通过这种策略，β-的两个片段d -mannosyl phosphomycoketide（Ç 32 -MPM）和四个stereopure 1,5- dimethylalkaneÇ 10个制备chirons。这些Ç 32个-MPM片段和C 10 chirons都表现出极大的潜在应用的构件块的含有手性oligoisoprenoid状链高度甲基支化的天然产物的合成。

  DOI：

  10.1016/j.tet.2013.09.020

文献信息

• Highly Stereocontrolled Total Synthesis of β-<scp>d</scp>-Mannosyl Phosphomycoketide: A Natural Product from <i>Mycobacterium tuberculosis</i>
  作者：Nan-Sheng Li、Louise Scharf、Erin J. Adams、Joseph A. Piccirilli

  DOI：10.1021/jo4006602

  日期：2013.6.21

  beta-D-Mannosyl phosphomycoketide (C-32-MPM), a naturally occurring glycolipid found in the cell walls of Mycobacterium tuberculosis, acts as a potent antigen to activate T-cells upon presentation by CD1c protein. The lipid portion of C-32-MPM contains, a C-32-mycoketide, consisting of a saturated oligoisoprenoid chain with five chiral methyl branches. Here we develop several stereocontrolled approaches to assemble the oligoisoprenoid chain with high stereopurity (>96%) using Julia-Kocienski olefinations followed by diimide reduction. By careful choice of olefination sites, we could derive all chirality from a single commercial compound, methyl (2S)-3-hydroxy-2-methylpropionate (>99% ee). Our approach is the first highly stereocontrolled method to prepare C-32-MPM molecule with >96% stereopurity from a single >99% ee starting material. We anticipate that our methods will facilitate the highly stereocontrolled synthesis of a variety of other natural products containing chiral oligoisoprenoid-like chains, including vitamins, phytol, insect pheromones, and archaeal lipids.
• Synthesis of stereopure acyclic 1,5-dimethylalkane chirons: building blocks of highly methyl-branched natural products
  作者：Nan-Sheng Li、Joseph A. Piccirilli

  DOI：10.1016/j.tet.2013.09.020

  日期：2013.11

  strategy, two fragments of β-d-mannosyl phosphomycoketide (C32-MPM) and four stereopure 1,5-dimethylalkane C10 chirons are prepared. These C32-MPM fragments and C10 chirons have shown great potential application as building blocks for the synthesis of highly methyl-branched natural products containing chiral oligoisoprenoid-like chains.

  朝stereopure一种有效的合成方法无环从甲基（2- 1,5- dimethylalkane积木- [R）-3-羟基-2-甲基丙酸酯（[R ）- 1（> 99％ee）和甲基（2-小号）-3-羟基2-甲基丙酸酯（小号） - 1（> 99％ee）的通过一系列的化学转化，包括朱莉娅- Kocienski烯和二酰亚胺还原的，被描述。通过这种策略，β-的两个片段d -mannosyl phosphomycoketide（Ç 32 -MPM）和四个stereopure 1,5- dimethylalkaneÇ 10个制备chirons。这些Ç 32个-MPM片段和C 10 chirons都表现出极大的潜在应用的构件块的含有手性oligoisoprenoid状链高度甲基支化的天然产物的合成。