Methanesulfonic acid (3R,7R,11S,15S)-16-(tert-butyl-dimethyl-silanyloxy)-3,7,11,15-tetramethyl-hexadecyl ester | 156593-00-9

• 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: Methanesulfonic acid (3R,7R,11S,15S)-16-(tert-butyl-dimethyl-silanyloxy)-3,7,11,15-tetramethyl-hexadecyl ester
• 英文别名: [(3R,7R,11S,15S)-16-[tert-butyl(dimethyl)silyl]oxy-3,7,11,15-tetramethylhexadecyl] methanesulfonate
• CAS: 156593-00-9
• 化学式: C₂₇H₅₈O₄SSi
• 分子量: 506.907
• InChiKey: HOVAVXGXEXEGTJ-ZJSPYRCASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.43
• 重原子数：
  33
• 可旋转键数：
  20
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  61
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methanesulfonic acid (3R,7R,11S,15S)-16-(tert-butyl-dimethyl-silanyloxy)-3,7,11,15-tetramethyl-hexadecyl ester 在 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 32.5h， 生成 1-O-Benzyl-2-O-[(3R,7R,11R)-3,7,11,15-tetramethylhexadecanyl]-3-O-[(3R,7R,11S,15S)-16-hydroxy-3,7,11,15-tetramethylhexadecanyl]-sn-glycerol
  参考文献：
  名称：

  Giant Vesicles from 72-Membered Macrocyclic Archæal Phospholipid Analogues: Initiation of Vesicle Formation by Molecular Recognition between Membrane Components

  摘要：

  Stereochemically pure archaeal acyclic bola-amphiphilic diphosphates 4 and 5, with the basic structure of the phospholipids found in Sulfolobus, have been synthesized for the first time. The self-assembly properties have been compared with those of the nearly identical 72-membered macrocyclic tetraether phosphates 3a and 3b, analogues of the major phospholipid components of Sulfolobus, Thermoplasma, and methanogenic Archaea, which were also synthesized. Phase contrast and fluorescence microscopies have shown that the dipolar lipids 1 and 2 spontaneously formed vesicles. Whereas the macrocyclic dipolar phosphates 3 spontaneously formed vesicles (phase contrast and fluorescence microscopies), the bolaform phosphate 4 gave only a lamellar structure (synchrotron diffraction pattern: repeat distance of about 4.25 nm but with only a few layers). However, upon addition of the unphosphorylated precursors phytanol, phytol, or geranylgeraniol to the acyclic lipids 4 and 5, giant vesicles were rapidly formed. Addition of n-hexadecanol or cholesterol did not lead to vesicle formation. Therefore it was concluded that this vesicle formation occurs only when the added molecule is closely compatible with the constituents of the lipid layer and can be inserted into the double layer. A slight mismatch (cholesterol or n-hexadecanol/polyprenyl chains) is therefore enough to block the insertion process presumably required for vesicle formation.

  DOI：

  10.1002/1521-3765(20000915)6:18<3351::aid-chem3351>3.0.co;2-4
• 作为产物：
  描述：

  (3S)-4-<(1-ethoxyethyl)oxy>-3-methylbutanenitrile 在 吡啶 、 咪唑 、 盐酸 、 六甲基磷酰三胺 、 正丁基锂 、 sodium amalgam 、 碘 、 lithium 、 二异丁基氢化铝 、 potassium carbonate 、 乙胺 、 三乙胺 、 间氯过氧苯甲酸 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 生成 Methanesulfonic acid (3R,7R,11S,15S)-16-(tert-butyl-dimethyl-silanyloxy)-3,7,11,15-tetramethyl-hexadecyl ester
  参考文献：
  名称：

  The first synthesis of an archaebacterial 36-membered macrocyclic diether lipid

  摘要：

  关键步骤是通过麦克马里偶联合成具有 36 元环的古细菌大环二元脂。

  DOI：

  10.1039/c39940000137

文献信息

• Total Synthesis of Archaeal 36-Membered Macrocyclic Diether Lipid
  作者：Tadashi Eguchi、Kenji Arakawa、Takumi Terachi、Katsumi Kakinuma

  DOI：10.1021/jo962327h

  日期：1997.4.1

  2 is reported. The synthesis is based upon stereoselective preparation of functionalized isoprenoid chains, ether-linkage formation between the isoprenoid chains with a glycerol derivative, and the ultimate intramolecular dicarbonyl coupling using low-valent titanium known as McMurry coupling. This synthetic method has successfully provided the first practical route to chemically defined archaeal macrocyclic

  报道了古细菌36元大环二醚脂质2的全合成。合成基于功能性异戊二烯链的立体选择性制备，异戊二烯链与甘油衍生物之间的醚键形成以及使用低价钛的最终分子内二羰基偶联（称为McMurry偶联）。这种合成方法成功地提供了化学上确定的古细菌大环膜脂质的第一个实用途径，由于缺乏合成途径，这些脂质无法获得。还描述了立体化学均一的古细菌双二十烷酰基甘油脂质的高度立体选择性和便利的合成。
• Total Synthesis of Archaeal 72-Membered Macrocyclic Tetraether Lipids
  作者：Tadashi Eguchi、Kazuya Ibaragi、Katsumi Kakinuma

  DOI：10.1021/jo972328p

  日期：1998.4.1

  Total synthesis of archaeal 72-membered macrocyclic tetraether lipids 3a and 3b is reported. The synthesis was principally composed of preparation of the functionalized half-sized diether compounds 11 and 15 first followed by appropriate dimerization through Julia coupling and final macrocyclization of the crucial dialdehydes 23 and 31 by McMurry coupling. This strategy appeared to be advantageous for the stereoselective synthesis of both natural 72-membered tetraether lipids 3a and 3b using common synthetic intermediates. In addition, this approach was so designed that its synthetic flexibility would allow construction of unnatural structural variants for physicochemical studies. Also described are the results of differential scanning calorimetric analysis of the synthesized lipids 3a and 3b. Both 3a and 3b showed almost the same phase behavior with the broad endothermic phase transition at -53 degrees C. The enthalpy of the phase transition, Delta H, was estimated to be 1.8 and 1.9 kcal/mol for 3a and 3b, respectively. The physicochemical as well as polymorphismic properties of 3a and 3b turned out to be indistinguishable despite of their regioisomeric structures. The physical structure of the phases in terms of the chemical structure is also discussed.
• Giant Vesicles from 72-Membered Macrocyclic Archæal Phospholipid Analogues: Initiation of Vesicle Formation by Molecular Recognition between Membrane Components
  作者：Tadashi Eguchi、Kenji Arakawa、Katsumi Kakinuma、Gert Rapp、Sangita Ghosh、Yoichi Nakatani、Guy Ourisson

  DOI：10.1002/1521-3765(20000915)6:18<3351::aid-chem3351>3.0.co;2-4

  日期：2000.9.15

  Stereochemically pure archaeal acyclic bola-amphiphilic diphosphates 4 and 5, with the basic structure of the phospholipids found in Sulfolobus, have been synthesized for the first time. The self-assembly properties have been compared with those of the nearly identical 72-membered macrocyclic tetraether phosphates 3a and 3b, analogues of the major phospholipid components of Sulfolobus, Thermoplasma, and methanogenic Archaea, which were also synthesized. Phase contrast and fluorescence microscopies have shown that the dipolar lipids 1 and 2 spontaneously formed vesicles. Whereas the macrocyclic dipolar phosphates 3 spontaneously formed vesicles (phase contrast and fluorescence microscopies), the bolaform phosphate 4 gave only a lamellar structure (synchrotron diffraction pattern: repeat distance of about 4.25 nm but with only a few layers). However, upon addition of the unphosphorylated precursors phytanol, phytol, or geranylgeraniol to the acyclic lipids 4 and 5, giant vesicles were rapidly formed. Addition of n-hexadecanol or cholesterol did not lead to vesicle formation. Therefore it was concluded that this vesicle formation occurs only when the added molecule is closely compatible with the constituents of the lipid layer and can be inserted into the double layer. A slight mismatch (cholesterol or n-hexadecanol/polyprenyl chains) is therefore enough to block the insertion process presumably required for vesicle formation.
• The first synthesis of an archaebacterial 36-membered macrocyclic diether lipid
  作者：Tadashi Eguchi、Takumi Terachi、Katsumi Kakinuma

  DOI：10.1039/c39940000137

  日期：——

  The archaebacterial macrocyclic diether lipid featuring a 36-membered ring is synthesized by the McMurry coupling as a key step.

  关键步骤是通过麦克马里偶联合成具有 36 元环的古细菌大环二元脂。