(5S)-<1'-<(tert-Butyldiphenylsilyl)oxy>ethyl>-2,2-cyclohexylidene-1,3-dioxolan-4-one | 153011-59-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (5S)-<1'-<(tert-Butyldiphenylsilyl)oxy>ethyl>-2,2-cyclohexylidene-1,3-dioxolan-4-one
• 英文别名: (5S)-{1'-[(tert-Butyldiphenylsilyl)oxy]ethyl}-2,2-cyclohexylidene-1,3-dioxolan-4-one；(S)-3-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-1,4-dioxaspiro[4.5]decan-2-one；(2S)-2-[2-[tert-butyl(diphenyl)silyl]oxyethyl]-1,4-dioxaspiro[4.5]decan-3-one
• CAS: 153011-59-7
• 化学式: C₂₆H₃₄O₄Si
• 分子量: 438.639
• InChiKey: CEUWXVYRUOPNRY-QHCPKHFHSA-N

物化性质

• 沸点：
  517.1±38.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.56
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (5S)-<1'-<(tert-Butyldiphenylsilyl)oxy>ethyl>-2,2-cyclohexylidene-1,3-dioxolan-4-one 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 dimethyl sulfide borane 、 sodium methylate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 (2S)-O-(tert-butyldiphenylsilyl)-1,2-epoxybutan-4-ol
  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：

  1,4-二氧杂螺[4.5]癸烷-2-乙酸,3-羰基-,(2S)- 在 咪唑 、 硼酸三甲酯 、 dimethyl sulfide borane 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 (5S)-<1'-<(tert-Butyldiphenylsilyl)oxy>ethyl>-2,2-cyclohexylidene-1,3-dioxolan-4-one
  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

• Verfahren zur Herstellung von Oxetanonen
  申请人：F. HOFFMANN-LA ROCHE AG

  公开号：EP0189577A2

  公开（公告）日：1986-08-06

  Verfahren zur Herstellung von die Pankreaslipase hemmenden Oxetanonäthylester der Formel worin X Undecyl oder 2Z,5Z,Undecadienyl, C6 n-Hexyl, Y lsobutyl und Z Formyl, oder Y Carbamoylmethyl und Z Acetyl sind, durch Veresterung entsprechender Oxetanonäthanolen, durch Hydrierung der 3-Undecenylgruppe zur Undecyigruppe X in entsprechenden Ausgangsoxetanonäthylester oder durch N-Formylierung oder N--Acetylierung von entsprechenden primären Aminen.

  制备抑制胰脂肪酶的氧杂环庚烷乙酯的方法，其化学式中X为十一烷基或2Z,5Z,十一二烯基，C6 n-己基，Y为异丁基和Z为甲酰基，或Y为氨基甲基和Z为乙酰基，通过对应的氧杂环庚烷醇的酯化，通过在相应的起始氧杂环庚烷乙酯中氢化3-十一烯基到X的十一烷基，或通过对应的初级胺的N-甲酰化或N-乙酰化实现。
• J. Org. Chem. 1993, 58, 7768-7781
  作者：

  DOI：——

  日期：——
• Drug. Future 1994, 19, 1003
  作者：

  DOI：——

  日期：——
• 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.