1-benzoxy-21-(tert-butyldiphenylsilyloxy)-(4R,8S,12R,16S,20S)-4,8,12,16,20-pentamethyl-5-(E/Z)-13-(E/Z)-heneicosa-5,13-diene | 1443233-28-0

• 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: 1-benzoxy-21-(tert-butyldiphenylsilyloxy)-(4R,8S,12R,16S,20S)-4,8,12,16,20-pentamethyl-5-(E/Z)-13-(E/Z)-heneicosa-5,13-diene
• CAS: 1443233-28-0
• 化学式: C₄₉H₇₄O₂Si
• 分子量: 723.211
• InChiKey: VJRFHZQPJVVMBM-ADNHOPRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.97
• 重原子数：
  52.0
• 可旋转键数：
  25.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-benzoxy-21-(tert-butyldiphenylsilyloxy)-(4R,8S,12R,16S,20S)-4,8,12,16,20-pentamethyl-5-(E/Z)-13-(E/Z)-heneicosa-5,13-diene 在 4-二甲氨基吡啶 、 2,4,6-三异丙基苯磺酰氯 、 溴化亚铜二甲硫醚 、 palladium 10% on activated carbon 、 四丁基氟化铵 、 氢气 、 氧气 、 sodium methylate 、 copper(II) sulfate 、 肼 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 乙醚 、 乙醇 、 氯仿 、 乙酸乙酯 为溶剂， 反应 63.5h， 生成 (4S,8S,12S,16S,20S)-4,8,12,16,20-pentamethylheptacosylphosphoryl-β-D-mannopyranoside
  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：

  8-(tert-butyldiphenylsilyloxy)-(3S,7R)-3,7-dimethyloctanal 在 四丁基氟化铵 、 戴斯-马丁氧化剂 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 1-benzoxy-21-(tert-butyldiphenylsilyloxy)-(4R,8S,12R,16S,20S)-4,8,12,16,20-pentamethyl-5-(E/Z)-13-(E/Z)-heneicosa-5,13-diene
  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