Methyl (E)-3-heptenoate | 54004-30-7

• 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)-3-heptenoate
• 英文别名: 3-Heptenoic acid, methyl ester, (E)-；methyl (E)-hept-3-enoate
• CAS: 54004-30-7
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: MELNJTLUIHVCHX-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2916190090

反应信息

• 作为反应物：
  描述：

  Methyl (E)-3-heptenoate 在 rhenium trioxide 、 双(三甲基硅基)过氧化物 、 水 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以90%的产率得到trans-2,3-epoxyheptanoic acid methyl ester
  参考文献：
  名称：

  无机氧鎓衍生物催化双（三甲基甲硅烷基）过氧化物进行烯烃环氧化。控制释放过氧化氢。

  摘要：

  用更便宜，更容易获得的无机rh氧化物（例如Re（2）O（7），ReO（3）（OH）和ReO）替代有机金属rh物种（例如CH（3）ReO（3）） （3））可以使用双（三甲基甲硅烷基）过氧化物（BTSP）作为氧化剂代替H（2）O（2）水溶液来完成。使用催化量的质子源，过氧化氢的受控释放有助于保留敏感的过氧化or物质，并使催化转化发生。该论文报道了对氧化or催化剂前体，底物范围以及各种添加剂对用BTSP烯烃环氧化的影响的系统研究。

  DOI：

  10.1021/jo010369m
• 作为产物：
  描述：

  2-羟基庚酸 在 三溴化磷 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 sodium iodide 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.0h， 生成 Methyl (E)-3-heptenoate
  参考文献：
  名称：

  Mohan, H Rama; Rao, A S, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1992, vol. 31, # 10, p. 698 - 700

  摘要：

  DOI：

文献信息

• Direct C–C Bond Formation of Allylic Alcohols with CO₂ toward Carboxylic Acids by Photoredox/Nickel Dual Catalysis
  作者：Zhengning Fan、Shenhao Chen、Song Zou、Chanjuan Xi

  DOI：10.1021/acscatal.2c00418

  日期：2022.3.4

  Carboxylation of allylic alcohols with carbon dioxide is accomplished by photoredox/nickel dual catalysis, generating linear acids exclusively with good Z/E stereoselectivity. Hantzsch ester is employed as the reductant instead of stoichiometric metallic reductants, and the reaction can be conducted under room temperature with a blue LED light source. Mechanistic studies reveal that the presence of

  烯丙醇与二氧化碳的羧基化是通过光氧化还原/镍双重催化完成的，仅生成具有良好Z/E立体选择性的线性酸。采用 Hantzsch 酯代替化学计量的金属还原剂作为还原剂，反应可以在室温下用蓝色 LED 光源进行。机理研究表明，该催化体系中水的存在对反应的成功至关重要，并且反应更有可能在原位形成的烯丙基碳酸氢盐的氧化加成中进行。
• Polymerization. XII. The Metalation of Olefins and Dienes and their Use in Alfin Polymerization of Butadiene¹
  作者：Avery A. Morton、Frank D. Marsh、Robert D. Coombs、Anne L. Lyons、Siegfried E. Penner、Hugh E. Ramsden、Vernon B. Baker、Ernest L. Little、Robert L. Letsinger

  DOI：10.1021/ja01164a125

  日期：1950.8
• Benner, Jill P.; Gill, G. Bryon; Parrott, Stephen J., Journal of the Chemical Society. Perkin transactions I, 1984, # 3, p. 331 - 342
  作者：Benner, Jill P.、Gill, G. Bryon、Parrott, Stephen J.、Wallace, Brian

  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.
• Ruthenium Complex-Catalyzed Carbonylation of Allylic Compounds
  作者：Take-aki Mitsudo、Nobuyoshi Suzuki、Teruyuki Kondo、Yoshihisa Watanabe

  DOI：10.1021/jo00104a036

  日期：1994.12

  Allylic alkyl carbonates are carbonylated under 40 atm of carbon monoxide at 100-120 degrees C in the presence of a catalytic amount of Ru-3(CO)(12)/1,10-phenanthroline to give alpha,beta- or beta,gamma-unsaturated esters in good to high yields. For example, cinnamyl methyl carbonate afforded the corresponding beta,gamma-unsaturated esters, methyl trans-4-phenyl-3-butenoate (1). in 93% yield. The regioselectivity in the carbonylation of crotyl methyl carbonate is unusual and it depends on the carbon monoxide pressure. The more sterically hindered carbon (gamma-carbon) is predominantly carbonylated at 20-50 atm. When the reaction of cinnamyl methyl carbonate was performed at elevated temperature (150 degrees C) without 1,10-phenanthroline, the dimer of 1, dimethyl 3-benzyl-2-(trans-2-phenylvinyl)glutarate, was obtained in 56% yield. In the presence of secondary amines, allylic alkyl carbonates were carbonylated mainly at alpha-carbon to give alpha,beta- or beta,gamma-unsaturated amides in high yields.