(1R,2S)-2-(methoxycarbonyl)-3,3-dimethyl-1-cyclopropanecarboxylic acid | 81873-51-0

• 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: (1R,2S)-2-(methoxycarbonyl)-3,3-dimethyl-1-cyclopropanecarboxylic acid
• 英文别名: (1R,3S)-3-methoxycarbonyl-2,2-dimethylcyclopropane-1-carboxylic acid
• CAS: 81873-51-0
• 化学式: C₈H₁₂O₄
• 分子量: 172.181
• InChiKey: LNIQYJXNDLAPKL-CRCLSJGQSA-N

物化性质

• 沸点：
  254.7±33.0 °C(Predicted)
• 密度：
  1.216±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  (1R,2S)-2-(methoxycarbonyl)-3,3-dimethyl-1-cyclopropanecarboxylic acid 在 sodium tetrahydroborate 、 草酰氯 、 水 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 乙酸乙酯 、 苯 为溶剂， 生成 (1S,5R)-3,6,6-trimethyl-3-azabicyclo[3.1.0]hexan-2-one
  参考文献：
  名称：

  Stereochemistry and chiroptical spectra of 3-azabicyclo[3.1.0]hexan-2-ones and thiones

  摘要：

  Several optically active substituted 3-azabicyclo[3.1.0]hexan-2-ones and their thiocarbonyl analogues have been synthesized, and their circular dichroism spectra studied. The crystal structure of thiolactam 1a showed that the bicyclic skeleton of the title compounds assumes a sofa-like geometry. It is postulated that the cyclopropyl moiety and amide or thioamide group constitute an inherently chiral chromophore, helicity of which determines the Cotton effect sign corresponding to the n-pi* electronic transition. The weak pi-pi* Cotton effect of thiolactams shows opposite sign to that observed for the lowest energy excitation. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00111-0
• 作为产物：
  描述：

  卡龙酸酐 在 吡啶 作用下， 反应 12.0h， 生成 (1R,2S)-2-(methoxycarbonyl)-3,3-dimethyl-1-cyclopropanecarboxylic acid
  参考文献：
  名称：

  Synthesis, stereochemistry, and chiroptical spectra of cyclopropyl lactones and thionolactones

  摘要：

  Several optically active substituted 3-oxabicyclo[3.1.0]hexan-2-ones and their thiocarbonyl analogues were synthesized, and their circular dichroism spectra are reported. It was found that the n-pi* Cotton effect sign is determined by the helicity of an inherently chiral chromophore formed by the lactone or thiolactone group and the cyclopropyl moiety. The pi-pi* Cotton effect of thiocarbonyl compounds shows opposite sign to that observed for the lowest energy transition. The crystal structures of two compounds were solved to establish their molecular geometries. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00419-3

文献信息

• Lewis Acid Catalyzed Enantioselective Photochemical Rearrangements on the Singlet Potential Energy Surface
  作者：Malte Leverenz、Christian Merten、Andreas Dreuw、Thorsten Bach

  DOI：10.1021/jacs.9b12068

  日期：2019.12.26

  The oxadi-π-methane rearrangement of 2,4-cyclohexadienones to bicyclic ketones was found to proceed with high enantioselectivity (92–97% ee) in the presence of catalytic amounts of a chiral Lewis acid (15 examples, 52–80% yield). A notable feature of the transformation is the fact that it proceeds on the singlet hypersurface and that no triplet intermediates are involved. Rapid racemic background reactions

  发现在催化量的手性路易斯酸（15 个例子，52-80% 产率）存在下，2,4-环己二烯酮的 oxadi-π-甲烷重排以高对映选择性（92-97% ee）进行）。转换的一个显着特征是它在单线态超曲面上进行并且不涉及三线态中间体。因此避免了快速的外消旋背景反应，并且催化剂负载可以保持低（10 mol%）。计算研究表明，通过锥形交叉点在路易斯酸结合的单线态中间体中确定对映选择性。该方法的实用性通过天然产物反菊酸的简洁合成得到了证明。
• Practical and Highly Enantioselective Ring Opening of Cyclic <i>Meso</i>-Anhydrides Mediated by Cinchona Alkaloids
  作者：Carsten Bolm、Ingo Schiffers、Christian L. Dinter、Arne Gerlach

  DOI：10.1021/jo000638t

  日期：2000.10.1

  The cinchona alkaloid-mediated opening of prochiral cyclic anhydrides in the presence of methanol leading to optically active hemiesters is described. Very structurally diverse anhydrides are converted into their corresponding methyl monoesters, and either enantiomer can be obtained with up to 99% ee by using quinine or quinidine as directing additive. After the reaction, the alkaloids can be recovered

  描述了在甲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。结构非常不同的酸酐被转化为其相应的甲基单酯，通过使用奎宁或奎尼丁作为直接添加剂，可以以高达99％ee的形式获得任何一种对映体。反应后，几乎可以定量回收生物碱并重新使用，而不会损失对映选择性。另外，提出了一种催化方案，该方案允许在容易获得的五甲基哌啶（哌啶）存在下亚化学计量使用奎尼丁。
• 2.1.1.5 The spatial distribution of earthquake foci
  作者：G. Schneider

  DOI：10.1007/10201917_18

  日期：——

  This document is part of Subvolume A of Volume 2 ‘Geophysics of the Solid Earth, the Moon and the Planets’ of Landolt-Börnstein - Group V Geophysics.

  该文档是《Landolt-Börnstein - V组地球物理学》第2卷《固体地球、月球和行星的地球物理学》子卷A的一部分。
• Enantioselective acyl-transfer catalysis by fluoride ions
  作者：Ryan Craig、Mili Litvajova、Sarah A. Cronin、Stephen J. Connon

  DOI：10.1039/c8cc05692g

  日期：——

  library of ad hoc designed bifunctional phase-transfer catalysts in which both the anion and the cation are directly involved in the reaction, the desymmetrisation of meso-succinic and -glutaric anhydrides is possible. 19F NMR spectroscopic studies support the intermediacy of an acyl fluoride intermediate.

  氟化物离子在碳基亲电试剂上的不对称亲核催化首次得到证明。使用临时设计的双功能相转移催化剂库，其中阴离子和阳离子都直接参与反应，内琥珀酸和戊二酸酐的不对称化是可能的。19 F NMR光谱研究支持酰基氟中间体的中间体。
• Stereoselective Hydrolysis of Substituted Cyclopropanedicarboxylates with Pig Liver Esterase
  作者：Paula Walser、Peter Renold、Victor N'Goka、Fatemeh Hosseinzadeh、Christoph Tamm

  DOI：10.1002/hlca.19910740832

  日期：1991.12.11

  hydrolysis of the meso-cyclopropane-1,2-dicarboxylates 1a-3a, 4, 5a, 6a, and 9, containing various substituents at C(3), and of the rac-3-phenylcyclopropane-1,2-dicarboxylates7a, 8a, and 10 with pig liver esterase (PLE) is described. The stereoselectivtty and absolute configurations of the products were determined. An interpretation of results was attempted on the basis of a recent active-site model for

  所述的水解的内消旋-环丙烷-1,2-二羧酸酯1A -图3a，4，图5a，图6a，和9中C，含各种取代基（3），和所述的外消旋-3-苯基环丙烷-1,2-二羧酸酯7A，图8a，和10与猪肝酯酶（PLE）进行说明。确定了产物的立体选择性和绝对构型。尝试根据最近的PLE活动站点模型来解释结果。