dimethyl 1,3-cuneanedicarboxylate | 30431-07-3

• 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: dimethyl 1,3-cuneanedicarboxylate
• CAS: 30431-07-3
• 化学式: C₁₂H₁₂O₄
• 分子量: 220.225
• InChiKey: SMMLCCHNYRMJKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.07
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  dimethyl 1,3-cuneanedicarboxylate 在 cesium hydroxide 、 水 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 dicesium cuneane-1,3-dicarboxylate
  参考文献：
  名称：

  立方烷在热水中通过立方烷异构化为半牛瓦烯

  摘要：

  摘要 笼型碳氢化合物支架（苯的潜在生物等排体）的构建通常涉及多个步骤，使得其选择性合成具有挑战性。然而，通过采用利用高度对称立方烷的异构化作为前体的支架编辑技术，可以用更少的步骤更有效地合成这些化合物。在这项研究中，我们提出了一种以 1,4-二甲酸二甲酯为原料，在热水中进行反应，选择性合成半布瓦烯-1,3-二甲酸的方法，且产率良好。

  DOI：

  10.1093/chemle/upad010
• 作为产物：
  描述：

  4-羟甲基立方烷羧酸甲酯 在 sodium periodate 、 rhodium(III) chloride hydrate 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 、 水 、 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 63.0h， 生成 dimethyl 1,3-cuneanedicarboxylate
  参考文献：
  名称：

  立方烷在热水中通过立方烷异构化为半牛瓦烯

  摘要：

  摘要 笼型碳氢化合物支架（苯的潜在生物等排体）的构建通常涉及多个步骤，使得其选择性合成具有挑战性。然而，通过采用利用高度对称立方烷的异构化作为前体的支架编辑技术，可以用更少的步骤更有效地合成这些化合物。在这项研究中，我们提出了一种以 1,4-二甲酸二甲酯为原料，在热水中进行反应，选择性合成半布瓦烯-1,3-二甲酸的方法，且产率良好。

  DOI：

  10.1093/chemle/upad010

文献信息

• Catalytic Asymmetric Synthesis of 2,6‐Disubstituted Cuneanes through Enantioselective Constitutional Isomerization of 1,4‐Disubstituted Cubanes
  作者：Hiyori Takebe、Seijiro Matsubara

  DOI：10.1002/ejoc.202200567

  日期：2022.10.7

  2,6-Substituted cuneanes were obtained by metal-catalyzed isomerization of 1,4-disubstituted cubanes and are stable cage-like hexahedral compounds with C2v symmetry. In this process, the chiral cage-like hexahedral hydrocarbon in one step. The asymmetric induction was performed using chiral P−C−P pincer Pd catalyst. The obtained cuneane will be a novel chiral scaffold.

  2,6-取代的立方烷是通过金属催化的1,4-二取代立方烷异构化得到的，是具有C 2 v对称性的稳定的笼状六面体化合物。在这一过程中，手性笼状六面体烃一步到位。使用手性 P-C-P 钳 Pd 催化剂进行不对称诱导。所获得的 cuneane 将是一种新型的手性支架。
• Biological Evaluation of Isosteric Applicability of 1,3‐Substituted Cuneanes as <i>m</i>‐Substituted Benzenes Enabled by Selective Isomerization of 1,4‐Substituted Cubanes
  作者：Kan Fujiwara、Shota Nagasawa、Ryusei Maeyama、Ryosuke Segawa、Noriyasu Hirasawa、Takatsugu Hirokawa、Yoshiharu Iwabuchi

  DOI：10.1002/chem.202303548

  日期：2024.2.21

  drug having m-substituted benzene moiety, was conducted. This study was inspired from the structural similarity of 1,3-substituted cuneanes with m-substituted benzene. Selective isomerization of 1,4-substituted cubanes into 1,3-substituted cuneanes enabled this evaluation. Biological evaluation of the synthesized analogs of ketoprofen and in silico study of the result of biological study revealed a potential

  对酮洛芬（一种具有间位取代的苯部分的抗炎药）的楔形类似物进行了生物学评价。这项研究的灵感来自于1,3位取代的楔烯与间位取代的苯的结构相似性。 1,4-取代的立方烷选择性异构化为1,3-取代的立方烷使得该评估成为可能。对合成的酮洛芬类似物的生物学评价以及生物学研究结果的计算机研究揭示了楔烷骨​​架在药物化学中作为间位取代苯的潜在等排用途。
• Silver(I)- and palladium(II)-catalyzed isomerizations of cubane. Synthesis and characterization of cuneane
  作者：Philip E. Eaton、Luigi Cassar、Jack Halpern

  DOI：10.1021/ja00724a061

  日期：1970.10
• Cubane, Cuneane, and Their Carboxylates:  A Calorimetric, Crystallographic, Calculational, and Conceptual Coinvestigation
  作者：Maria Victoria Roux、Juan Z. Dávalos、Pilar Jiménez、Rafael Notario、Obis Castaño、James S. Chickos、William Hanshaw、Hui Zhao、Nigam Rath、Joel F. Liebman、Behzad S. Farivar、A. Bashir-Hashemi

  DOI：10.1021/jo050471+

  日期：2005.7.1

  This study is a multinational, multidisciplinary contribution to the thermochemistry of dimethyl1,4-cubanedicarboxylate and the corresponding isomeric, cuneane derivative and provides both structural and thermochemical information regarding the rearrangement of dimethyl 1,4cubanedicarboxylate to dimethyl 2,6-cuneanedicarboxylate. The enthalpies of formation in the condensed phase at T = 298.15 K of dimethyl 1,4-cubanedicarboxylate (dimethyl pentacyclo[4.2.0.0.(2,5)0.(3.8)0(4,7) octane-1,4-dicarboxylate) and dimethyl 2,6-cuneanedicarboxylate (dimethyl pentacyclo[3.3.0.0.(2,4)0.(3,7)0(6,8)]octane-2,6-dicarboxylate) have been determined by combustion calorimetry, Delta H-f degrees(m)(cr)/k.J(.) =232.62 +/- 5.84 and -413.02 +/- 5.16, respectively. The enthalpies of sublimation have been evaluated by combining vaporization enthalpies evaluated by correlation-gas chromatography and fusion enthalpies measured by differential scanning calorimetry and adjusted to T = 298.15 K, Delta H-g(cr)m (298.15 K)/kJ (.) mol(-1) = 117.2 +/- 3.9 and 106.8 +/- 3.0, respectively. Combination of these two enthalpies resulted in Delta H-f degrees(m)(g., 298.15 K)/kJ (.) mol(-1) of -115.4 +/- 7.0 for dimethyl 1,4-cubanedicarboxylate and -306.2 +/- 6.0 for dimethyl 2,6-cuneanedicarboxylate. These measurements, accompanied by quantum chemical calculations, resulted in values of Delta H-f(m)(g, 298.15 K) = 613.0 +/- 9.5 kJ (.) mol(-1) for cubane and 436.4 +/- 8.8 kJ (.) mol(-1) for cuneane. From these enthalpies of formation, strain enthalpies of 681.0 +/- 9.8 and 504.4 +/- 9.1 kJ (.) mol(-1) were calculated for cubane and cuneane by means of isodesmic reactions, respectively. Crystals of dimethyl 2,6-cuneanedicarboxylate are disordered; the substitution pattern and structure have been confirmed by determination of the X-ray crystal structure of the corresponding diacid.