8-(tert-butyldiphenylsilyloxy)-(3S,7R)-3,7-dimethyloctanal | 1443233-19-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 8-(tert-butyldiphenylsilyloxy)-(3S,7R)-3,7-dimethyloctanal
• 英文别名: (3S,7R)-8-[tert-butyl(diphenyl)silyl]oxy-3,7-dimethyloctanal
• CAS: 1443233-19-9
• 化学式: C₂₆H₃₈O₂Si
• 分子量: 410.672
• InChiKey: AJOBAOIUHIEMBY-XZOQPEGZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.59
• 重原子数：
  29
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  8-(tert-butyldiphenylsilyloxy)-(3S,7R)-3,7-dimethyloctanal 在 palladium 10% on activated carbon 、 四丁基氟化铵 、 氢气 、 氧气 、 戴斯-马丁氧化剂 、 copper(II) sulfate 、 lithium hexamethyldisilazane 、 肼 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 18.0h， 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：

  8-benzyloxy-1-(tert-butyldiphenylsilyloxy)-(2R,6S)-2,6-dimethyloctane 在 palladium 10% on activated carbon 、 氢气 、 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 3.0h， 生成 8-(tert-butyldiphenylsilyloxy)-(3S,7R)-3,7-dimethyloctanal
  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