ethyl 2(E)-4-<(tert-butyldimethylsilyl)oxy>pentenoate | 105198-40-1

• 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: ethyl 2(E)-4-<(tert-butyldimethylsilyl)oxy>pentenoate
• 英文别名: ethyl trans-4-((tert-butyldimethylsilyl)oxy)-2-pentenoate；ethyl (E)-4-(tert-butyldimethylsiloxy)pent-2-enoate；ethyl trans-4-[(tert-butyldimethylsilyl)oxy]-2-pentenoate；ethyl (E)-4-[tert-butyl(dimethyl)silyl]oxypent-2-enoate
• CAS: 105198-40-1
• 化学式: C₁₃H₂₆O₃Si
• 分子量: 258.433
• InChiKey: JIPMHCMBHMJNGC-MDZDMXLPSA-N

物化性质

• 沸点：
  285.5±23.0 °C(Predicted)
• 密度：
  0.914±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 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 2(E)-4-<(tert-butyldimethylsilyl)oxy>pentenoate 在 四丁基氟化铵 作用下， 生成 ethyl trans-4-hydroxy-2-pentenoate
  参考文献：
  名称：

  Stereoselective radical additions of γ-oxy-α,β-unsaturated ester derivatives; 1,2-asymmetric induction in acyclic and cyclisation systems

  摘要：

  Examination was made of 1,2-asymmetric induction in the addition of alkyl radicals to gamma-oxy-alpha,beta-unsaturated ester derivatives 1 and 2 prepared from ethyl lactate and (R)-2,3-0-isopropylideneglyceraldehyde 3, respectively. The addition reactions of hexyl, cyclohexyl and 3-phenylpropyl radicals to (Z)-2 derived from aldehyde 3 gave beta-addition products with syn-stereoselectivity (syn:anti = 8.6:1-syn only). The reactions of (E)-2 were non-stereoselective. Based on allylic strain, a transition-state model for the syn-stereoselectivity is proposed. 1,2-Asymmetric induction was carried out in radical cyclisation to synthesize optically active cyclohexane derivatives.

  DOI：

  10.1039/p19950000271
• 作为产物：
  描述：

  (S)-(-)-ethyl 2-(tert-butyldimethylsilyloxy)propanoate 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.25h， 生成 ethyl 2(E)-4-<(tert-butyldimethylsilyl)oxy>pentenoate
  参考文献：
  名称：

  通过使用新的霍纳-埃蒙斯试剂（乙基二芳基膦酸酯）乙酸乙酯，高度选择性地合成Z-不饱和酯。

  摘要：

  由膦酸三乙酯，PCl（5）和相应的酚制备新的Horner-Emmons试剂（二芳基膦酸乙酯）乙酸乙酯1。在Triton B或NaH存在下，THF中1与几种醛的反应表明，这些试剂可用于合成Z-不饱和酯。在所检查的试剂中，发现乙基（二-邻甲苯基膦酰基）-，[双（邻乙基苯基）膦基]-和[双（邻异丙基苯基）膦基]乙酸酯（1k-m）最有效，得到Z-不饱和酯，选择性为93-99％。

  DOI：

  10.1021/jo970057c

文献信息

• Yamamoto, Yoshinori; Chounan, Yukiyasu; Nishii, Shinji, Journal of the American Chemical Society, 1992, vol. 114, # 20, p. 7652 - 7660
  作者：Yamamoto, Yoshinori、Chounan, Yukiyasu、Nishii, Shinji、Ibuka, Toshiro、Kitahara, Haruo

  DOI：——

  日期：——
• An improved procedure for the two carbon homologation of esters to α, β-unsaturated esters
  作者：James M. Takacs、Mark A. Helle、Franklin L. Seely

  DOI：10.1016/s0040-4039(00)84232-x

  日期：1986.1
• TAKACS, J. M.;HELLE, M. A.;SEELY, F. L., TETRAHEDRON LETT., 1986, 27, N 11, 1257-1260
  作者：TAKACS, J. M.、HELLE, M. A.、SEELY, F. L.

  DOI：——

  日期：——
• Highly Selective Synthesis of <i>Z</i>-Unsaturated Esters by Using New Horner−Emmons Reagents, Ethyl (Diarylphosphono)acetates
  作者：Kaori Ando

  DOI：10.1021/jo970057c

  日期：1997.4.1

  New Horner-Emmons reagents, ethyl (diarylphosphono)acetates 1, were prepared from triethyl phosphonoacetate, PCl(5), and the corresponding phenols. The reaction of 1 with several kinds of aldehydes in the presence of Triton B or NaH in THF solvent revealed that these reagents are useful for the synthesis of Z-unsaturated esters. Among the reagents examined, ethyl(di-o-tolylphosphono)-, [bis(o-ethylphenyl)phosphono]-

  由膦酸三乙酯，PCl（5）和相应的酚制备新的Horner-Emmons试剂（二芳基膦酸乙酯）乙酸乙酯1。在Triton B或NaH存在下，THF中1与几种醛的反应表明，这些试剂可用于合成Z-不饱和酯。在所检查的试剂中，发现乙基（二-邻甲苯基膦酰基）-，[双（邻乙基苯基）膦基]-和[双（邻异丙基苯基）膦基]乙酸酯（1k-m）最有效，得到Z-不饱和酯，选择性为93-99％。
• Stereoselective radical additions of γ-oxy-α,β-unsaturated ester derivatives; 1,2-asymmetric induction in acyclic and cyclisation systems
  作者：Tsutomu Morikawa、Yoshiaki Washio、Susumu Harada、Ryo Hanai、Takashi Kayashita、Hisako Nemoto、Motoo Shiro、Takeo Taguchi

  DOI：10.1039/p19950000271

  日期：——

  Examination was made of 1,2-asymmetric induction in the addition of alkyl radicals to gamma-oxy-alpha,beta-unsaturated ester derivatives 1 and 2 prepared from ethyl lactate and (R)-2,3-0-isopropylideneglyceraldehyde 3, respectively. The addition reactions of hexyl, cyclohexyl and 3-phenylpropyl radicals to (Z)-2 derived from aldehyde 3 gave beta-addition products with syn-stereoselectivity (syn:anti = 8.6:1-syn only). The reactions of (E)-2 were non-stereoselective. Based on allylic strain, a transition-state model for the syn-stereoselectivity is proposed. 1,2-Asymmetric induction was carried out in radical cyclisation to synthesize optically active cyclohexane derivatives.