ethyl (4Z,6S)-6-<(tert-butyldiphenylsilyl)oxy>-4-heptenoate | 161040-07-9

• 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: ethyl (4Z,6S)-6-<(tert-butyldiphenylsilyl)oxy>-4-heptenoate
• 英文别名: (S,Z)-ethyl 6-((tert-butyldiphenylsilyl)oxy)hept-4-enoate；ethyl (Z,6S)-6-[tert-butyl(diphenyl)silyl]oxyhept-4-enoate
• CAS: 161040-07-9
• 化学式: C₂₅H₃₄O₃Si
• 分子量: 410.629
• InChiKey: MPAYLAJFJRRGEM-ROOORRATSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.85
• 重原子数：
  29
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (4Z,6S)-6-<(tert-butyldiphenylsilyl)oxy>-4-heptenoate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以86%的产率得到(S,Z)-ethyl 6-((tert-butyldiphenylsilyl)oxy)hept-4-enoate
  参考文献：
  名称：

  δ-Unsaturated γ-amino acids: enantiodivergent synthesis and cell imaging studies

  摘要：

  报告通过对映异构 [3,3]-sigmatropic 重排策略合成了δ-不饱和δ-氨基酸的两种对映体。在该策略中观察到对映体过量率大于 94% 的优异对映体。通过活细胞成像评估了一种荧光氨基酸衍生物的细胞渗透性。

  DOI：

  10.1039/c3cc40824h
• 作为产物：
  描述：

  (-)-(2S)-methyl 2-(tert-butyldiphenylsilyloxy)propanoate 在 sodium hexamethyldisilazane 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 ethyl (4Z,6S)-6-<(tert-butyldiphenylsilyl)oxy>-4-heptenoate
  参考文献：
  名称：

  Activation of the reverse-Cope elimination by allylic oxygen functions: Syntheses of (−)-hygroline and (+)-pseudohygroline

  摘要：

  Reverse-Cope cyclisations of N-(4-alkenyl)hydroxylamines 8 are accelerated by the presence of the allylic oxygen function; this has been applied to a brief synthesis of the alkaloids (-)-hygroline 6 and (+)-pseudohygroline 7 (C) 1999 Elsevier Science Ltd. Ali rights reserved.

  DOI：

  10.1016/s0040-4039(99)01131-4

文献信息

• Stereoselective synthesis of tetrahydrofurans using intramolecular oxymercurations
  作者：Agatha Garavelas、Irene Mavropoulos、Patrick Perlmutter、Gunnar Westman

  DOI：10.1016/0040-4039(94)02287-l

  日期：1995.1

  The influence of alkene geometry and remote substitution on the stereochemical outcome of intramolecular oxymercurations leading to five-membered rings is described.

  描述了烯烃的几何形状和远程取代对导致五元环的分子内氧化汞的立体化学结果的影响。
• Remote Allylic Silyloxy Groups as Stereocontrol Elements in Intramolecular Oxymercurations of γ-Hydroxyalkenes
  作者：Katharina Bratt、Agatha Garavelas、Patrick Perlmutter、Gunnar Westman

  DOI：10.1021/jo951853q

  日期：1996.1.1

  The diastereoselectivity in intramolecular oxymercurations of gamma-hydroxyalkenes bearing a remote allylic oxy substituent has been investigated, It was found that the best selectivity was obtained by employing a combination of (Z)-alkene geometry and a tert-butyldiphenylsilyl protecting group attached to the remote allylic oxygen as in 4a-g. Cyclization, using mercuric acetate in dichloromethane, of all the (Z)-alkenols gave the syn, diastereomer, 5a-g, as the major product. For example, cyclization of 4b gave syn diastereomer 5b and anti diastereomer 6b in a ratio of 7:1. It was found that this ratio could be improved by replacing dichloromethane with acetonitrile. Under these conditions the ratio of 5b to 6b increased to 19:1. Cyclization of (E)-alkene 9 gave very poor diastereoselection. These syn-selective intramolecular oxymercurations were exploited in enantioselective syntheses of two diastereomers of methyl nonactate.