endo-cis-2-carboxy-3-(ethoxycarbonyl)bicyclo<2.2.1>hept-5-ene | 1187951-16-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: endo-cis-2-carboxy-3-(ethoxycarbonyl)bicyclo<2.2.1>hept-5-ene
• 英文别名: (+/-)-norborn-5-ene-2endo,3endo-dicarboxylic acid monoethyl ester；(+/-)-Norborn-5-en-2endo,3endo-dicarbonsaeure-monoaethylester；2-Ethyl (1S,2R,3S,4R)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate；(1R,2S,3R,4S)-3-ethoxycarbonylbicyclo[2.2.1]hept-5-ene-2-carboxylic acid
• CAS: 1187951-16-1
• 化学式: C₁₁H₁₄O₄
• 分子量: 210.23
• InChiKey: KQOXZRIHIPLKJD-UYXSQOIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  endo-cis-2-carboxy-3-(ethoxycarbonyl)bicyclo<2.2.1>hept-5-ene 在 吡啶 、 lithium aluminium tetrahydride 、 氯化亚砜 、 双氧水 作用下， 以 甲醇 、 乙醚 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 70.5h， 生成 endo-2-methylene-3-[[(p-toluenesulfonyl)oxy]methyl]bicyclo[2.2.1]hept-5-ene
  参考文献：
  名称：

  Synthesis of the D2d-dinoradamantane derivatives having two coaxially oriented unsaturated centers. 6-Methylene-D2d-dinoradamantan-2-one and D2d-dinoradamantane-2,6-dione

  摘要：

  DOI：

  10.1021/jo00139a017
• 作为产物：
  描述：

  diethyl (endo,endo)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate 在 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 72.0h， 以82.9%的产率得到endo-cis-2-carboxy-3-(ethoxycarbonyl)bicyclo<2.2.1>hept-5-ene
  参考文献：
  名称：

  在二烷基双环[2.2.1]庚-5-烯-2,3-二羧酸酯单水解反应中观察到新的外切/内切选择性

  摘要：

  几个外切或内切二甲基或二乙基双环[2.2.1]庚-5-烯-2,3-二羧酸酯的新的单水解反应显示出对外-羰基烷氧基单水解的更高选择性，尽管反应中心位于远离降冰片烯环的位置。

  DOI：

  10.1016/j.tetlet.2003.09.131

文献信息

• An alkaloid-mediated desymmetrization of meso-anhydrides via a nucleophilic ring opening with benzyl alcohol and its application in the synthesis of highly enantiomerically enriched β-amino acids
  作者：Carsten Bolm、Ingo Schiffers、Iuliana Atodiresei、Christian P.R. Hackenberger

  DOI：10.1016/s0957-4166(03)00579-2

  日期：2003.11

  permits the isolation of the products in analytically pure form and the recovery of the alkaloids almost quantitatively. These hemiesters can be converted to N-protected β-amino esters by means of Curtius degradation of the corresponding acyl azides. Subsequent cleavage of both protecting groups by a single reaction step leads to the free β-amino acids in excellent yields. The efficiency of this procedure

  描述了在苄醇存在下金鸡纳生物碱介导的前手性环酐的打开，导致旋光性半酯。通过使用奎宁或奎尼丁作为导向添加剂，将结构多样的酸酐转化为相应的苄基单酯，其中对映异构体的ee最高可达99％。一个简单的水后处理方案可以分离出分析纯形式的产物，并几乎定量地回收生物碱。这些半个学期可以转换为N-通过相应的酰基叠氮化物的库尔蒂斯降解来保护-β-氨基酯。随后通过单个反应步骤裂解两个保护基团以优异的产率得到游离的β-氨基酸。通过短时不对称合成杀真菌剂顺-喷他汀来证明该方法的效率，所述顺式-喷他霉素递送氨基酸的对映体过量> 99.7％。
• Potential Antimicrobial Agents. III. 4-Methylamino-2,4-alkadienoic Acid γ-Lactams¹
  作者：HENRY M. WALTON

  DOI：10.1021/jo01354a025

  日期：1957.3
• Schneider, Hans-Joerg; Sangwan, Naresh K., Angewandte Chemie, 1987, vol. 99, # 9, p. 924 - 925
  作者：Schneider, Hans-Joerg、Sangwan, Naresh K.

  DOI：——

  日期：——
• A Novel Cost-Effective Thiourea Bifunctional Organocatalyst for Highly Enantioselective Alcoholysis of<i>meso</i>-Cyclic Anhydrides: Enhanced Enantioselectivity by Configuration Inversion
  作者：Su-Xi Wang、Fen-Er Chen

  DOI：10.1002/adsc.200800761

  日期：2009.3

  Abstractmagnified imageA novel inexpensive thiourea bifunctional organocatalyst which can promote the highly enantioselective (up to 95% ee) alcoholysis of meso‐cyclic anhydrides has been developed. Computational studies on the catalytic process as well as a synthetic application of this new catalyst are also presented.
• Highly Enantioselective Ring Opening of Cyclic <i>Meso</i>-Anhydrides to Isopropyl Hemiesters with Ti−TADDOLates:  An Alternative to Hydrolytic Enzymes?
  作者：Georg Jaeschke、Dieter Seebach

  DOI：10.1021/jo971731t

  日期：1998.2.1

  The Lewis acid mediated transfer of an alkoxide ligand from the chiral ligand sphere of Ti-TADDOLate (1) to cyclic meso anhydrides to afford the corresponding hemiesters is described. By using this method a variety of structurally different anhydrides can be converted to isopropyl hemiesters with high enantioselectivities (enantiomer ratios up to 99:1). We have also investigated Lewis acidic titanium complexes, which differ from 1 in the chiral ligand or the alkoxide ligand that is transferred. Finally, a catalytic version, which allows the substoichiometric use of Ti-TADDOLate in the presence of stoichiometric amounts of Al(Oi-Pr)(3), is presented.