methyl (E)-2-(trimethylsilyl)-2-heptenoate | 132539-41-4

• 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: methyl (E)-2-(trimethylsilyl)-2-heptenoate
• 英文别名: methyl (E)-2-trimethylsilylhept-2-enoate
• CAS: 132539-41-4
• 化学式: C₁₁H₂₂O₂Si
• 分子量: 214.38
• InChiKey: WGQYBILWWSCPBQ-MDZDMXLPSA-N

物化性质

• 沸点：
  75-80 °C(Press: 1 Torr)
• 密度：
  0.883±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  methyl (E)-2-(trimethylsilyl)-2-heptenoate 在 四丁基氟化铵 、 水 、 lithium diisopropyl amide 作用下， 反应 5.5h， 生成 methyl (E)-2-butyl-2-heptenoate
  参考文献：
  名称：

  (Z)-.alpha.-(trimethylsilyl) .alpha.,.beta.-unsaturated esters. Their stereoselective conversion into .alpha.,.beta.- and .beta.,.gamma.-unsaturated esters and .beta.,.gamma.-unsaturated ketene acetals

  摘要：

  Deprotonation of methyl (Z)-alpha-(trimethylsilyl) alpha,beta-unsaturated esters with lithium diisopropylamide (LDA) or with lithium hexamethyldisilazide (LHMDS) in the presence of hexamethylphosphoramide (HMPA) as an activator, followed by protonation of the intermediate dienolates with methanol, produces stereoselectively the desilylated (E)-3-alkenoic esters. Trapping the dienolates with chlorotrimethylsilane instead of methanol and then treatment of the resultant ketene acetals with aqueous hydrochloric acid affords (E)-alpha-(trimethylsilyl)-beta,gamma-alkenoic esters in 98% isomeric purities. In the absence of HMPA, (Z)-alpha-(trimethylsilyl)-alpha, beta-alkenoic esters undergo a Michael-type addition with LDA to furnish, after methanol-mediated elimination of the diisopropylamine moiety, (E)-alpha-(trimethylsilyl)-alpha,beta-alkenoic esters. In contrast to the behavior with the corresponding Z esters, deprotonation of the E esters with LDA does not require an activator. Treatment of the dienolate intermediates formed with chlorotrimethylsilane yields (O-methyl-C,O-bis(trimethylsilyl)ketene acetals, and alkylation furnishes (E)-alpha-alkyl beta,gamma-unsaturated esters. Protodesilylation of the latter compounds with tetra-n-butylammonium fluoride followed by hydrolytic workup provides trisubstituted 2-alkenoates.

  DOI：

  10.1021/jo00007a039
• 作为产物：
  描述：

  1-三甲基硅烷-1-己炔 在 甲醇 、 三氟化硼乙醚 、 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 反应 23.67h， 生成 methyl (E)-2-(trimethylsilyl)-2-heptenoate
  参考文献：
  名称：

  (Z)-.alpha.-(trimethylsilyl) .alpha.,.beta.-unsaturated esters. Their stereoselective conversion into .alpha.,.beta.- and .beta.,.gamma.-unsaturated esters and .beta.,.gamma.-unsaturated ketene acetals

  摘要：

  Deprotonation of methyl (Z)-alpha-(trimethylsilyl) alpha,beta-unsaturated esters with lithium diisopropylamide (LDA) or with lithium hexamethyldisilazide (LHMDS) in the presence of hexamethylphosphoramide (HMPA) as an activator, followed by protonation of the intermediate dienolates with methanol, produces stereoselectively the desilylated (E)-3-alkenoic esters. Trapping the dienolates with chlorotrimethylsilane instead of methanol and then treatment of the resultant ketene acetals with aqueous hydrochloric acid affords (E)-alpha-(trimethylsilyl)-beta,gamma-alkenoic esters in 98% isomeric purities. In the absence of HMPA, (Z)-alpha-(trimethylsilyl)-alpha, beta-alkenoic esters undergo a Michael-type addition with LDA to furnish, after methanol-mediated elimination of the diisopropylamine moiety, (E)-alpha-(trimethylsilyl)-alpha,beta-alkenoic esters. In contrast to the behavior with the corresponding Z esters, deprotonation of the E esters with LDA does not require an activator. Treatment of the dienolate intermediates formed with chlorotrimethylsilane yields (O-methyl-C,O-bis(trimethylsilyl)ketene acetals, and alkylation furnishes (E)-alpha-alkyl beta,gamma-unsaturated esters. Protodesilylation of the latter compounds with tetra-n-butylammonium fluoride followed by hydrolytic workup provides trisubstituted 2-alkenoates.

  DOI：

  10.1021/jo00007a039

文献信息

• NAJAFI, M. RAMIN;WANG, MEI-LING;ZWEIFEL, GEORGE, J. ORG. CHEM., 56,(1991) N, C. 2468-2476
  作者：NAJAFI, M. RAMIN、WANG, MEI-LING、ZWEIFEL, GEORGE

  DOI：——

  日期：——
• (Z)-.alpha.-(trimethylsilyl) .alpha.,.beta.-unsaturated esters. Their stereoselective conversion into .alpha.,.beta.- and .beta.,.gamma.-unsaturated esters and .beta.,.gamma.-unsaturated ketene acetals
  作者：M. Ramin Najafi、Mei Ling Wang、George Zweifel

  DOI：10.1021/jo00007a039

  日期：1991.3

  Deprotonation of methyl (Z)-alpha-(trimethylsilyl) alpha,beta-unsaturated esters with lithium diisopropylamide (LDA) or with lithium hexamethyldisilazide (LHMDS) in the presence of hexamethylphosphoramide (HMPA) as an activator, followed by protonation of the intermediate dienolates with methanol, produces stereoselectively the desilylated (E)-3-alkenoic esters. Trapping the dienolates with chlorotrimethylsilane instead of methanol and then treatment of the resultant ketene acetals with aqueous hydrochloric acid affords (E)-alpha-(trimethylsilyl)-beta,gamma-alkenoic esters in 98% isomeric purities. In the absence of HMPA, (Z)-alpha-(trimethylsilyl)-alpha, beta-alkenoic esters undergo a Michael-type addition with LDA to furnish, after methanol-mediated elimination of the diisopropylamine moiety, (E)-alpha-(trimethylsilyl)-alpha,beta-alkenoic esters. In contrast to the behavior with the corresponding Z esters, deprotonation of the E esters with LDA does not require an activator. Treatment of the dienolate intermediates formed with chlorotrimethylsilane yields (O-methyl-C,O-bis(trimethylsilyl)ketene acetals, and alkylation furnishes (E)-alpha-alkyl beta,gamma-unsaturated esters. Protodesilylation of the latter compounds with tetra-n-butylammonium fluoride followed by hydrolytic workup provides trisubstituted 2-alkenoates.