methyl (1S,2R)-2-carbonochloridoylcyclohexane-1-carboxylate

• 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: methyl (1S,2R)-2-carbonochloridoylcyclohexane-1-carboxylate
• 化学式: C₉H₁₃ClO₃
• 分子量: 204.653
• InChiKey: OIJFGMIBHPAXAF-RQJHMYQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (1S,2R)-2-carbonochloridoylcyclohexane-1-carboxylate 以 乙醚 为溶剂， 生成 (-)-(3S,5R,15R,20R)-5-methylyohimbane
  参考文献：
  名称：

  5-甲基育亨班八种非对映异构体的合成及构象分析

  摘要：

  Some time ago, Siddiqui et al. proposed structure 1 for the naturally occurring indole alkaloid yohambinine, which they had isolated from Rauwolfia serpentine BENTH. In the present paper, enantioselective syntheses of all eight diastereoisomers endowed with the proposed 5-methylyohimbane structure are disclosed. However, none of the synthetically prepared compounds showed spectroscopic properties identical with those reported for the natural product yohambinine, which, therefore, must possess an altogether different constitutional formula. The ground-state conformations of the diastereoisomers 1, 14, 18, 19, 21, 22, 25, and 26 were deduced by spectroscopic methods, and the outcome was compared with the results of extensive force-field, semi-empirical, and ab-initio calculations.

  DOI：

  10.1002/1522-2675(200203)85:3<945::aid-hlca945>3.0.co;2-a
• 作为产物：
  描述：

  (1S,2R)-2-(methoxycarbonyl)cyclohexanecarboxylic acid 在 草酰氯 作用下， 反应 0.67h， 生成 methyl (1S,2R)-2-carbonochloridoylcyclohexane-1-carboxylate
  参考文献：
  名称：

  5-甲基育亨班八种非对映异构体的合成及构象分析

  摘要：

  Some time ago, Siddiqui et al. proposed structure 1 for the naturally occurring indole alkaloid yohambinine, which they had isolated from Rauwolfia serpentine BENTH. In the present paper, enantioselective syntheses of all eight diastereoisomers endowed with the proposed 5-methylyohimbane structure are disclosed. However, none of the synthetically prepared compounds showed spectroscopic properties identical with those reported for the natural product yohambinine, which, therefore, must possess an altogether different constitutional formula. The ground-state conformations of the diastereoisomers 1, 14, 18, 19, 21, 22, 25, and 26 were deduced by spectroscopic methods, and the outcome was compared with the results of extensive force-field, semi-empirical, and ab-initio calculations.

  DOI：

  10.1002/1522-2675(200203)85:3<945::aid-hlca945>3.0.co;2-a

文献信息

• 1,2-Cyclomethylencarboxylic monoamide hydroxamic derivatives. A novel class of non-amino acid angiotensin converting enzyme inhibitors
  作者：Luigi Turbanti、Guido Cerbai、Cristina Di Bugno、Raffaello Giorgi、Giorgio Garzelli、Marco Criscuoli、Anna R. Renzetti、Alessandro Subissi、Giancarlo Bramanti、Scott A. DePriest

  DOI：10.1021/jm00058a006

  日期：1993.3

  2-cyclopentanedicarboxylic acids bearing either a carboxylic, sulfhydrylic, or hydroxamic group in the side chain were synthesized and evaluated in vitro for their inhibitory activity against angiotensin converting enzyme. The compounds were designed as potential ACE inhibitors of novel structure, assuming that a monoamidic residue of an 1,2-cyclomethylenedicarboxylic acid could be an alternative structure

  合成了一系列在侧链带有羧基，巯基或异羟肟基的顺式和反式1,2-环己烷二羧酸和1,2-环戊烷二羧酸的单酰胺衍生物，并在体外评估了它们对血管紧张素转化的抑制活性酶。假定1,2-环亚甲基二羧酸的单酰胺残基可以作为酰基脯氨酸部分（各种ACE抑制剂共有的羧基末端部分）的替代结构，这些化合物可被设计为新型结构的潜在ACE抑制剂。在环己烷系列的异羟肟酸酯衍生物中发现活性最高的化合物。在这一系列衍生物中，效力的显着增加是由于酰胺氮与甲基或乙基的烷基化所致。因此，通过两种不同的手性合成途径制备了顺式和反式-1,2-环己烷二甲酸异羟肟酸衍生物的对映异构体，并在体外评估了它们的ACE抑制剂效能。发现在经典的ACE抑制剂中，顺式系列（21a，21c）和反式系列（16b，16d）的活性对映体都具有在C-2处的所有R构型和在C-1处的R或S构型。活性必须严格要求在末端羧酸盐（对应于我们化合物的C-1）处具有S构型。该
• Highly Enantioselective Desymmetrization of <i>Meso</i> Anhydrides by a Bifunctional Thiourea-Based Organocatalyst at Low Catalyst Loadings and Room Temperature
  作者：Aldo Peschiulli、Yurii Gun'k、Stephen J. Connon

  DOI：10.1021/jo702639h

  日期：2008.3.1

  Bifunctional (thio)urea-based cinchona alkaloid derivatives have been shown to promote highly efficient enantioselective desymmetrization reactions of meso anhydrides. The most selective of these catalysts is capable of the enantioselective methanolysis of succinic and glutaric anhydride derivatives to form hemiester products with >90% yield and enantiomeric excess at 1 mol % loading and ambient temperature

  官能（硫代）脲基金鸡纳生物碱衍生物已经显示出促进高效的对映选择性desymmetrization反应内消旋酸酐。这些催化剂中最具选择性的是能够对琥珀酸和戊二酸酐衍生物进行对映选择性甲醇水解，以> 90％的收率和在1 mol％的负载量和环境温度下形成对映体过量的半酯产物。
• Cinchona alkaloid derivative modified Fe₃O₄ nanoparticles for enantioselective ring opening of <i>meso</i>-cyclic anhydrides
  作者：Sanjiv O. Tomer、Hemant P. Soni

  DOI：10.1039/d1nj04081b

  日期：——

  and it was used as a capping agent during the synthesis of Fe3O4 NPs. The resulting modified quinidine capped Fe3O4 (Fe3O4@mQD) NPs were characterized by different techniques and used for enantioselective ring opening (ERO) by methanolysis in a heterogeneous mode of catalysis. The interactions of mQD with the Fe3O4 surface, as well as its % loading, were studied using FTIR spectroscopy and thermal analysis

  在目前的工作中，奎尼丁的分子骨架在喹啉部分的 C6' 碳的甲氧基官能团上被一个长链羧酸基团 (-COOH) 修饰，并在合成过程中用作封端剂。 Fe 3 O 4纳米粒子。所得修饰的奎尼丁封端的 Fe 3 O 4 (Fe 3 O 4 @mQD) NPs 通过不同的技术进行了表征，并在多相催化模式下通过甲醇分解用于对映选择性开环 (ERO)。mQD 与 Fe 3 O 4的相互作用使用 FTIR 光谱和热分析技术研究了表面及其负载百分比。优化了溶剂系统、温度和底物等反应参数。在 Fe 3 O 4 @mQD NPs存在下通过甲醇分解对琥珀酸和戊二酸酐进行 ERO 。优化后的方案可以产生具有高对映选择性（高达 98% ee）和出色产率（大多数情况下超过 90%）的手性半酯。
• Synthesis and Characterization of Novel Aminophosphine Ligands Based on Ferrocenodecaline Backbones
  作者：Max Weißenbacher、Thomas Sturm、Hermann Kalchhauser、Christoph Kratky、Walter Weissensteiner

  DOI：10.1007/s007060200069

  日期：2002.7

   Novel aminophosphine ligands for enantioselective transition metal catalysts based on different ferroceno cis - and trans -decaline backbones were synthesized and structurally characterized. Their palladium dichloride complexes were tested in the asymmetric Grignard cross coupling reaction of vinyl bromide and phenylethyl magnesium chloride, but only very low enantioselectivities were obtained. Steric

  合成了 新型的氨基膦配体，用于基于不同的二茂铁 顺 -和 反- 癸啉骨架的对映选择性过渡金属催化剂， 并对其结构进行了表征。在乙烯基溴与苯乙基氯化镁的不对称 格利雅（Grignard） 交叉偶联反应中测试了它们的二氯化钯配合物 ，但仅获得非常低的对映选择性。氨基膦配体中的立体应变导致严重的骨架变形，另外导致各个二甲基氨基的旋转变慢，如通过可变温度NMR光谱法检测到的。
• 1,2-Disubstituted cyclohexane derived tripeptide aldehydes as novel selective thrombin inhibitors
  作者：Nicholas J.S. Harmat、Cristina Di Bugno、M. Criscuoli、Raffaello Giorgi、Annalisa Lippi、Adriano Martinelli、Susanna Monti、A. Subissi

  DOI：10.1016/s0960-894x(98)00200-5

  日期：1998.5

  A series of tripeptide arginine aldehydes was synthesized by replacement of proline with 1,2-disubstituted cyclohexane derivatives in the sequence of D-MePhe-Pro-Arg-H. Based on molecular modeling, further modification of the D-MePhe residue resulted in a potent and selective thrombin inhibitor.

  通过用D-MePhe-Pro-Arg-H序列中的1，2-二取代的环己烷衍生物代替脯氨酸，合成了一系列的三肽精氨酸醛。基于分子模型，D-MePhe残基的进一步修饰产生了有效的选择性凝血酶抑制剂。