(3S,5R)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-hexadecanoic acid | 1026461-21-1

• 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,5R)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-hexadecanoic acid
• 英文别名: (3S,5R)-3-[tert-butyl(dimethyl)silyl]oxy-5-phenylmethoxyhexadecanoic acid
• CAS: 1026461-21-1
• 化学式: C₂₉H₅₂O₄Si
• 分子量: 492.815
• InChiKey: UTHLUDPSFIBOGK-SXOMAYOGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.75
• 重原子数：
  34
• 可旋转键数：
  20
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3S,5R)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-hexadecanoic acid 在 palladium on activated charcoal 吡啶 、 氢氧化钾 、 氢氟酸 、 氢气 、 苯磺酰氯 、 三苯基膦 、 lithium diisopropyl amide 、 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 、 乙腈 为溶剂， 反应 13.33h， 生成 奥利司他
  参考文献：
  名称：

  Total synthesis of (-)-tetrahydrolipstatin

  摘要：

  The total synthesis of (-)-tetrahydrolipstatin utilizing two approaches is described. In the first, L-malic acid was used as a chiral template to obtain enantiomerically pure (R)-3-(benzyloxy)-tetradecanal (11) which was chain-extended using 1-(trimethylsilyl)-2-nonene and a Lewis acid. This advanced intermediate was further elaborated to the target compound in good overall yield. The second approach utilized lauraldehyde as a starting material and capitalizes on an asymmetric allylboronation (91 % ee). The product could be obtained enantiomerically pure by conversion to the (R)-acetoxymandelate ester and hydrolysis. Oxidative cleavage of the terminal double bond led to 11 which was further extended using 1,3- and 1,2-asymmetric induction based on existing neighboring chirality. The synthesis of tetrahydrolipstatin using the second approach comprises seven steps from 11 and proceeds in 38 % overall yield.

  DOI：

  10.1021/jo00079a022
• 作为产物：
  描述：

  (4S,6R)-6-(Benzyloxy)-4-<(tert-butyldimethylsilyl)oxy>-1-heptadecane 在 sodium chlorite 、 sodium dihydrogenphosphate 、 二甲基硫 、 臭氧 、 三乙胺 作用下， 以 水 、 叔丁醇 为溶剂， 反应 4.5h， 生成 (3S,5R)-5-Benzyloxy-3-(tert-butyl-dimethyl-silanyloxy)-hexadecanoic acid
  参考文献：
  名称：

  Total synthesis of (-)-tetrahydrolipstatin

  摘要：

  The total synthesis of (-)-tetrahydrolipstatin utilizing two approaches is described. In the first, L-malic acid was used as a chiral template to obtain enantiomerically pure (R)-3-(benzyloxy)-tetradecanal (11) which was chain-extended using 1-(trimethylsilyl)-2-nonene and a Lewis acid. This advanced intermediate was further elaborated to the target compound in good overall yield. The second approach utilized lauraldehyde as a starting material and capitalizes on an asymmetric allylboronation (91 % ee). The product could be obtained enantiomerically pure by conversion to the (R)-acetoxymandelate ester and hydrolysis. Oxidative cleavage of the terminal double bond led to 11 which was further extended using 1,3- and 1,2-asymmetric induction based on existing neighboring chirality. The synthesis of tetrahydrolipstatin using the second approach comprises seven steps from 11 and proceeds in 38 % overall yield.

  DOI：

  10.1021/jo00079a022

文献信息

• Total synthesis of (-)-tetrahydrolipstatin
  作者：Stephen Hanessian、Ashok Tehim、Ping Chen

  DOI：10.1021/jo00079a022

  日期：1993.12

  The total synthesis of (-)-tetrahydrolipstatin utilizing two approaches is described. In the first, L-malic acid was used as a chiral template to obtain enantiomerically pure (R)-3-(benzyloxy)-tetradecanal (11) which was chain-extended using 1-(trimethylsilyl)-2-nonene and a Lewis acid. This advanced intermediate was further elaborated to the target compound in good overall yield. The second approach utilized lauraldehyde as a starting material and capitalizes on an asymmetric allylboronation (91 % ee). The product could be obtained enantiomerically pure by conversion to the (R)-acetoxymandelate ester and hydrolysis. Oxidative cleavage of the terminal double bond led to 11 which was further extended using 1,3- and 1,2-asymmetric induction based on existing neighboring chirality. The synthesis of tetrahydrolipstatin using the second approach comprises seven steps from 11 and proceeds in 38 % overall yield.