trans-1,4-Endomethylen-cyclohexan-dicarbonsaeure-(2,3)

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: trans-1,4-Endomethylen-cyclohexan-dicarbonsaeure-(2,3)
• 英文别名: (+/-)-norbornane-2endo,3exo-dicarboxylic acid；(+/-)-Norbornan-2endo,3exo-dicarbonsaeure；(+/-)-Norbornan-dicarbonsaeure-(2endo.3exo)；(1S,2R,3R,4R)-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid
• 化学式: C₉H₁₂O₄
• 分子量: 184.192
• InChiKey: IVVOCRBADNIWDM-XZBKPIIZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  74.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-1,4-Endomethylen-cyclohexan-dicarbonsaeure-(2,3) 在 乙酰氯 作用下， 生成 cis-5-norbornene-endo-2,3-dicarboxylic anhydride
  参考文献：
  名称：

  Alder; Stein, Justus Liebigs Annalen der Chemie, 1933, vol. 504, p. 216,232, 252

  摘要：

  DOI：
• 作为产物：
  描述：

  Dimethyl norbornane-trans-2,3-dicarboxylate 在 氢氧化钾 作用下， 生成 trans-1,4-Endomethylen-cyclohexan-dicarbonsaeure-(2,3)
  参考文献：
  名称：

  Einfache Darstellung von ?5-cyclohexen-2,3-trans-dicarbons�ureesrtern

  摘要：

  DOI：

  10.1007/bf00909956

文献信息

• Palladium-Catalyzed Double Activation and Arylation of 2° and 3° C(sp3)–H Bonds of the Norbornane System: Formation of a C–C Bond at the Bridgehead Carbon and Bridgehead Quaternary Stereocenter
  作者：Srinivasarao Babu、Ramarao Parella

  DOI：10.1055/s-0033-1341242

  日期：——

  Pd-catalyzed activation and direct arylation of both 2° and the bridgehead 3° (sp3) C–H bonds and an unprecedented C–C bond formation at the bridgehead carbon of the norbornane system are reported. The assembly of bridgehead-substituted norbornane frameworks having contiguous stereocenters was accomplished. X-ray crystal structure analysis of representative molecules unambiguously established the stereochemistry

  据报道，Pd 催化的 2° 和桥头 3°（sp3）C-H 键的活化和直接芳基化以及在降冰片烷系统的桥头碳上形成了前所未有的 C-C 键。完成了具有连续立体中心的桥头取代降冰片烷骨架的组装。代表性分子的 X 射线晶体结构分析明确地建立了立体化学。
• Direct synthesis of macrodiolides via hafnium(<scp>iv</scp>) catalysis
  作者：Mylène de Léséleuc、Shawn K. Collins

  DOI：10.1039/c5cc03586d

  日期：——

  Efficient direct synthesis of macrodiolides via catalysis using Hf(OTf)₄ is possible in high yields, forming water as the sole by-product.

  通过使用Hf(OTf)₄催化剂，可以高产率地直接合成大环二酯，形成水作为唯一副产物。
• On the enhancement of stereoselection by cooperation between chiral auxiliaries. Asymmetric diels-alder reactions with fumaric acid bis ((S)-proline benzyl ester) amide
  作者：H. Waldmann、M. Dräger

  DOI：10.1016/s0040-4039(01)80696-1

  日期：1989.1

  Fumaric acid bis ((S)-proline benzyl ester) amide reacts with cyclopentadiene in thermal and Lewis acid catalyzed Diels-Alder reactions to give the cycloadducts with high yields and diastereomeric ratios up to 100:1.

  富马酸双（（S）-脯氨酸苄酯）酰胺在热和路易斯酸催化的狄尔斯-阿尔德反应中与环戊二烯反应，以高收率和高达100：1的非对映异构体比例提供环加合物。
• (1<i>S</i>,2<i>R</i>,3<i>R</i>,4<i>R</i>)-α,α,α′,α′-Tetraphenylbicyclo [2.2.1]heptane-2,3-dimethanol and Its Enantiomer as Ligands in Titanate-Complex-Catalyzed Diethylzinc Addition to Aldehydes
  作者：Claus Dreisbach、Udo Kragl、Christian Wandrey

  DOI：10.1055/s-1994-25600

  日期：——

  Starting from (1S,2R,3R,4R)-bicyclo[2.2.1]heptane-2,3-dicarboxylic acid (1) and its enantiomer ent-1 the title compounds 3 and ent-3 were synthesized in 74% yield. They were used in asymmetric synthesis for the first time. The titanate-complex-catalyzed addition of diethylzinc to aldehydes was chosen as a model system for testing the catalytic properties of 3. The resulting alcohols 4 could be obtained with up to 97.7% enantiomeric excess.

  从(1S,2R,3R,4R)-双环[2.2.1]庚烷-2,3-二羧酸(1)及其对映体ent-1出发，合成了标题化合物3和ent-3，产率为74%。它们首次用于不对称合成。选择钛酸盐络合物催化的二乙基锌与醛的加成反应作为测试化合物3催化特性的模型系统。得到的醇4的对映体过量可高达97.7%。
• A novel asymmetric synthesis of highly enantiomerically enriched norbornane-type diamine derivatives
  作者：Carsten Bolm、Ingo Schiffers、Iuliana Atodiresei、Salih Ozcubukcu、Gerhard Raabe

  DOI：10.1039/b206943c

  日期：2003.1.8

  The simple and highly enantioselective methanolysis of norbornene dicarboxylic acid anhydride mediated by quinidine leads to the corresponding cis-monomethyl ester with 98% ee. By means of selective ester epimerization, followed by Curtius degradation of the intermediate trans-diacyl azide, two optically active norbornane-type diamines are obtained as their hydrochloric salts. Liberating the amine

  简单且高度对映选择性 甲醇分解 的 降冰片烯 二羧酸酐介导 奎尼丁导致相应的顺式-单甲酯的ee为98％。通过选择性酯差向异构化，然后Curtius降解中间的反式二叠氮叠氮化物，两种光学活性降冰片烷型二胺以其盐酸盐形式获得。解放胺 与过量 三乙胺 原位及后续衍生化提供潜在的C 1不对称配体 不对称催化，收率极高。