methyl (Z)-2-(trimethylsilyl)-2-heptenoate | 79439-14-8

• 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 (Z)-2-(trimethylsilyl)-2-heptenoate
• 英文别名: methyl (Z)-2-trimethylsilylhept-2-enoate
• CAS: 79439-14-8
• 化学式: C₁₁H₂₂O₂Si
• 分子量: 214.38
• InChiKey: WGQYBILWWSCPBQ-KTKRTIGZSA-N

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 (Z)-2-(trimethylsilyl)-2-heptenoate 在 甲醇 、 六甲基磷酰三胺 、 四丁基氟化铵 、 水 、 lithium diisopropyl amide 作用下， 反应 7.0h， 生成 methyl (E)-2-methyl-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 三氟化硼乙醚 、 二异丁基氢化铝 作用下， 反应 21.5h， 生成 methyl (Z)-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

• A CONVENIENT STEREOSPECIFIC SYNTHESIS OF α,β-UNSATURATED CARBOXYLIC ESTERS VIA THE PALLADIUM-CATALYZED CARBONYLATION OF 1-ALKENYLBORANES
  作者：Norio Miyaura、Akira Suzuki

  DOI：10.1246/cl.1981.879

  日期：1981.7.5

  1-Alkenyiboranes readily prepared by the hydroboration of alkynes react smoothly with carbon monoxide in the presence of palladium chloride and sodium acetate in methanol to give the corresponding α,β-unsaturated carboxylic esters with retention of configuration with respect to alkenylboranes in good yields.

  通过烷炔的氢硼化容易制备的1-烯基硼烷在甲醇中与煤气反应，存在氯化铂和醋酸钠，可以顺利生成相应的α,β-不饱和羧酸酯，并保持与烯基硼烷的构象一致，产率良好。
• 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：——
• MIYAURA NORIO; SUZUKI AKIRA, CHEM. LETT., 1981, NO 7, 879-882
  作者：MIYAURA NORIO、 SUZUKI AKIRA

  DOI：——

  日期：——