(6Z,8E,10E,14Z)-(3R,5S,12R)-3,12-Bis-(tert-butyl-diphenyl-silanyloxy)-5-hydroxy-icosa-6,8,10,14-tetraenoic acid methyl ester | 158800-23-8

• 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: (6Z,8E,10E,14Z)-(3R,5S,12R)-3,12-Bis-(tert-butyl-diphenyl-silanyloxy)-5-hydroxy-icosa-6,8,10,14-tetraenoic acid methyl ester
• CAS: 158800-23-8
• 化学式: C₅₃H₇₀O₅Si₂
• 分子量: 843.307
• InChiKey: AZAJPKRWRQFNOI-WQWWZHPOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.39
• 重原子数：
  60.0
• 可旋转键数：
  22.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  64.99
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (6Z,8E,10E,14Z)-(3R,5S,12R)-3,12-Bis-(tert-butyl-diphenyl-silanyloxy)-5-hydroxy-icosa-6,8,10,14-tetraenoic acid methyl ester 在 四丁基氟化铵 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以81%的产率得到3(R)-hydroxyleukotriene B₄ methyl ester
  参考文献：
  名称：

  3-Hydroxyleukotriene B4 (3-OH-LTB4): Total Synthesis and Stereochemical Assignment.

  摘要：

  The asymmetric total synthesis of 3-hydroxyleukotriene B-4 (3-OH-LTB(4)), an ethanol-inducible proinflammatory autacoid, was achieved using a triply convergent strategy for the sequential union of propargylic arsonium salt 3 with pyranosides 2a,b and furanose 4. Both saccharide subunits were derived from commercial 2-deoxy-D-ribose. The key transformation involved palladium-mediated coupling of bromoacetylenide 9 with stannylglycal 6a,b. Subsequent Rieke zinc hydrogenation of acetylene 10a,b and controlled ionic reduction of the cross-conjugated cyclic enol ether using NaBH3CN at pH similar to 4-4.5 established the cis-Delta(6,7)-olefin and C(5)-hydroxyl stereochemistry, respectively, and led to 11a,b. Methyllactol hydrolysis, PCC oxidation, methanolysis, and desilylation afforded 3(R)- and 3(S)-OH-LTB(4) methyl esters, respectively. On the basis of chromatographic and mass spectral comparisons, enzymatically derived 3-OH-LTB(4) is composed principally of the 3(S)-isomer (>95%).

  DOI：

  10.1021/ja00091a004
• 作为产物：
  描述：

  在 aluminum oxide 、 三乙胺 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (6Z,8E,10E,14Z)-(3R,5S,12R)-3,12-Bis-(tert-butyl-diphenyl-silanyloxy)-5-hydroxy-icosa-6,8,10,14-tetraenoic acid methyl ester
  参考文献：
  名称：

  3-Hydroxyleukotriene B4 (3-OH-LTB4): Total Synthesis and Stereochemical Assignment.

  摘要：

  The asymmetric total synthesis of 3-hydroxyleukotriene B-4 (3-OH-LTB(4)), an ethanol-inducible proinflammatory autacoid, was achieved using a triply convergent strategy for the sequential union of propargylic arsonium salt 3 with pyranosides 2a,b and furanose 4. Both saccharide subunits were derived from commercial 2-deoxy-D-ribose. The key transformation involved palladium-mediated coupling of bromoacetylenide 9 with stannylglycal 6a,b. Subsequent Rieke zinc hydrogenation of acetylene 10a,b and controlled ionic reduction of the cross-conjugated cyclic enol ether using NaBH3CN at pH similar to 4-4.5 established the cis-Delta(6,7)-olefin and C(5)-hydroxyl stereochemistry, respectively, and led to 11a,b. Methyllactol hydrolysis, PCC oxidation, methanolysis, and desilylation afforded 3(R)- and 3(S)-OH-LTB(4) methyl esters, respectively. On the basis of chromatographic and mass spectral comparisons, enzymatically derived 3-OH-LTB(4) is composed principally of the 3(S)-isomer (>95%).

  DOI：

  10.1021/ja00091a004