(2S,3R)-3-endo-isopropoxycarbonyl-bicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid | 173657-15-3

• 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: (2S,3R)-3-endo-isopropoxycarbonyl-bicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid
• 英文别名: bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monoisopropyl ester；(1R,2S,3R,4S)-3-propan-2-yloxycarbonylbicyclo[2.2.1]hept-5-ene-2-carboxylic acid
• CAS: 173657-15-3
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: YPLRAQYWVXRZHI-QCLAVDOMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (2S,3R)-3-endo-isopropoxycarbonyl-bicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid 在 盐酸 、 三乙基硼氢化锂 作用下， 生成 (3aS,4R,7S,7aR)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one
  参考文献：
  名称：

  Highly Enantioselective Ring Opening of Cyclic Meso-Anhydrides to Isopropyl Hemiesters with Ti−TADDOLates:  An Alternative to Hydrolytic Enzymes?

  摘要：

  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.

  DOI：

  10.1021/jo971731t
• 作为产物：
  描述：

  titanium(IV)isopropoxide 、 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride 在 polymer-bound TADDOL 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 216.0h， 生成 (2S,3R)-3-endo-isopropoxycarbonyl-bicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid
  参考文献：
  名称：

  催化（和化学计量）对映选择性反应中与聚合物和树状聚合物结合的TiTADDOLates：五配位阳离子Ti络合物是否具有催化活性？

  摘要：

  α，α，α'，α'- Ť ETRA一个RYL -1,3- d ioxolane -4,5- d imethan醇S中的杂环的，或在（TADDOLs），含苯乙烯基基团或者在C（2）用通常的方法（18-22、24、25）准备α位。这些化合物与苯乙烯和二乙烯基苯在悬浮液中共聚，生成呈颗粒状分布的聚合物（33–40，方案3），粒径分布相当均匀（150–45μm），在普通有机溶剂中可溶胀。还制备了HOCH 2-和BrCH 2取代的TADDOL，并用于连接到Merrifield树脂或树状分子上（23，26–32）。这些材料中的TADDOL部分易于形成Ti（和Al）络合物（方案4），可用作聚合物或树状聚合物结合的试剂（化学计量）或路易斯酸（催化）。用这些新的手性助剂研究的反应是：对醛（R 2 Zn和RTi（OCHMe 2）3；方案5，表1）和酮（LiAlH 4，表2）的对映选择性亲核加成；内消旋酸酐的对

  DOI：

  10.1002/hlca.19960790621

文献信息

• Solvent-Free Asymmetric Anhydride Opening in a Ball Mill
  作者：Toni Rantanen、Ingo Schiffers、Carsten Bolm

  DOI：10.1021/op6002743

  日期：2007.5.1

  The mechanochemical technique of ball milling has been applied to the asymmetric opening of meso-anhydrides, mediated by the cinchona alkaloid quinidine. A simple workup procedure affords the products, optically active dicarboxylic acid monoesters, in high yields, with up to 64% ee. With most substrates no column chromatography was needed. A range of various alcohols, as well as anhydrides, reacted

  球磨的机械化学技术已应用于由金鸡纳生物碱奎尼丁介导的内消旋酸酐的不对称打开。一个简单的后处理程序可以以高收率提供高达64％ee的旋光二羧酸单酯产物。对于大多数底物，无需柱色谱法。各种醇和酸酐反应良好，因此证明了该方法的范围。即使是纯固体成分的混合物也会发生反应，并且不需要溶剂（后处理期间除外）。与标准溶液反应相比，几乎等摩尔量的起始原料的可能使用大大简化了产物分离。
• Diorganotin complexes of carboxylates: synthesis and characterization
  作者：Asha Chilwal、Gagan Deep、Priti Malhotra、A.K. Narula

  DOI：10.1080/00958972.2013.775428

  日期：2013.3.1

  Diorganotin complexes of monoisopropyl and monomethyl nadiate, succinate, and phthalate were synthesized and characterized by elemental analysis, FT-IR, H-1 NMR, C-13 NMR, and Sn-119 NMR spectroscopic techniques. The spectroscopic investigation demonstrated that carboxylate is bidentate in the diorganotin complexes. On the basis of (1)J(Sn-119-C-13) and (2)J(Sn-119-H-1) values, C-Sn-C bond angles were also calculated. The newly synthesized complexes were also screened for their antibacterial activities against Gram-positive and Gram-negative pathogenic strains of bacteria.
• 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.
• Seebach, Dieter; Jaeschke, Georg; Wang, Yan Ming, Angewandte Chemie, 1995, vol. 107, # 21, p. 2605 - 2606
  作者：Seebach, Dieter、Jaeschke, Georg、Wang, Yan Ming

  DOI：——

  日期：——
• Synthesis of 3,5,7-Trioxapentacyclo[7.2.1.0^2,8.0^4,11.0^6,10]dodecane. A Novel Diacetal Trioxa-Cage
  作者：Shih-Hwa Tsai、Hsien-Jen Wu、Wen-Sheng Chung

  DOI：10.1002/jccs.199600064

  日期：1996.10

  Abstract3,5,7‐Trioxapentacyclo[7.2.1.02,8.04,11.06,10]dodecane, the parent compound of novel diacetal trioxa‐cages, was synthesized from maleic anhydride cyclopentadiene adduct 1 by a four‐step sequence. Attempts for the synthesis of monoaza dioxa‐cage 12 failed. Ozonolysis of compound 9 in CH2Cl2‐EtOH(1:1) at −78°C followed by reduction with Me2S gave 13 in 65% yield.