(-)-(2R,3S)-3-hydroxy-2-methyl-3-phenylpropanoic acid | 36041-79-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: (-)-(2R,3S)-3-hydroxy-2-methyl-3-phenylpropanoic acid
• 英文别名: (2R,3S)-3-hydroxy-2-methyl-3-phenylpropanoic acid
• CAS: 36041-79-9
• 化学式: C₁₀H₁₂O₃
• 分子量: 180.203
• InChiKey: JWISPMMVFLKFMW-APPZFPTMSA-N

物化性质

• 熔点：
  96-97 °C
• 沸点：
  331.7±30.0 °C(Predicted)
• 密度：
  1.213±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-(2R,3S)-3-hydroxy-2-methyl-3-phenylpropanoic acid 在 吡啶 作用下， 以 四氯化碳 、 乙醚 为溶剂， 反应 15.08h， 生成 methyl (2R,3S,2'S)-3--2-methyl-3-phenylpropionate
  参考文献：
  名称：

  Jephcote, Vincent J.; Pratt, Andrew J.; Thomas, Eric J., Journal of the Chemical Society. Perkin transactions I, 1989, p. 1529 - 1535

  摘要：

  DOI：
• 作为产物：
  描述：

  (2R,3S)-3-Hydroxy-2-methyl-3-phenyl-propionic acid (1R,2S)-2-[methyl-(1,2,3,4,5,6,7,8-octahydro-anthracene-9-sulfonyl)-amino]-1-phenyl-propyl ester 生成 (-)-(2R,3S)-3-hydroxy-2-methyl-3-phenylpropanoic acid
  参考文献：
  名称：

  的程度顺式-选择性为羧酸酯的硼介导的不对称醛醇缩合反应

  摘要：

  为顺式选择性羟醛缩合反应的新的手性试剂已经被开发了基于最近的发现，即羧酸酯的硼介导的醛醇缩合反应的立体化学通过该酯的醇部分的膨松度的控制，通过适当选择试剂，并受烯醇化条件的影响。这种易于获得的廉价试剂已被用于大环内酯单萜内酯的合成研究中。

  DOI：

  10.1016/s0040-4039(98)00123-3

文献信息

• (<i>E</i>)-2-Boryl-1,3-butadiene Derivatives of the 10-TMS-9-BBDs: Highly Selective Reagents for the Asymmetric Synthesis of <i>anti-</i>1,2-Disubstituted 3,4-Pentadien-1-ols
  作者：Javier R. González、Ana Z. González、John A. Soderquist

  DOI：10.1021/ja9047202

  日期：2009.7.29

  The efficient stepwise construction of optically pure trans-4-substituted 2-boryl-1,3-butadienes 6 is described. Hydroboration of 1-alkynes with either enantiomeric form of 3 leads to the pure trans-1-alkenylboranes 4 which undergo addition of alpha-ethoxyvinyllithium followed by a BF(3)-mediated 1,2-B-->C vinylic group migration to provide 6. These organoboranes 6 serve as a new type of asymmetric

  描述了光学纯反式-4-取代的 2-boryl-1,3-丁二烯 6 的有效逐步构建。1-炔烃与 3 的任一对映体形式的硼氢化反应导致纯的反式-1-烯基硼烷 4 加入 α-乙氧基乙烯基锂，然后由 BF(3) 介导的 1,2-B-->C 乙烯基迁移到提供 6。这些有机硼烷 6 作为一种新型的不对称烯丙基硼化试剂，为制备作为对映体纯形式的基本上单一的非对映异构体的抗 1,2-二取代 3,4-戊二烯-1-醇 8 提供了极具选择性的方案。顺式-2-硼基-1,3-丁二烯 (9) 的一个例子是通过格利雅程序制备的。发现提供了相应的合成醇 11。
• Triazolium Carbene Catalysts and Stereoselective Bond Forming Reactions Thereof
  申请人：Rovis Tomislav

  公开号：US20110224431A1

  公开（公告）日：2011-09-15

  Provided herein are triazolium carbine catalysts useful for asymmetric hydration, fluorination, and deuteration, and processes for their preparation. Also provided are synthetic reactions in which these catalysts are used, in particular, in stereoselective formation of carbon-chlorine, carbon-hydrogen, carbon-fluorine, and carbon-deuterium bonds.

  本文提供了用于不对称水合、氟化和重氢化的三唑碳催化剂，以及它们的制备方法。还提供了在这些催化剂中使用的合成反应，特别是在碳-氯、碳-氢、碳-氟和碳-氘键的立体选择性形成中使用的反应。
• Sterically Hindered Chiral Ferrocenyl P,N,N-Ligands for Highly Diastereo-/Enantioselective Ir-Catalyzed Hydrogenation of α-Alkyl-β-ketoesters via Dynamic Kinetic Resolution
  作者：Chuan-Jin Hou、Xiang-Ping Hu

  DOI：10.1021/acs.orglett.6b02828

  日期：2016.11.4

  A new class of sterically hindered chiral ferrocenyl P,N,N-ligands have been prepared through a two-step transformation from (Sc,Rp)-PPFNH2, in which a new (R)-stereogenic center at the pyridinylmethyl position was generated in high diastereoselectivity. With these newly developed P,N,N-ligands, Ir-catalyzed asymmetric hydrogenation of various α-alkyl-substituted β-aryl-β-ketoesters via dynamic kinetic

  通过从（S c，R p）-PPFNH 2的两步转化制备了新型的空间位阻性手性二茂铁基二茂铁基P，N，N-配体，其中在吡啶基甲基位置上有一个新的（R）-立体异构中心产生的非对映异构体选择性高。借助这些新开发的P，N，N配体，首次在高非对映体和对映体选择性下，通过动态动力学拆分实现了Ir催化的各种α-烷基取代的β-芳基-β-酮酸酯的不对称氢化，导致了多种光学活性的反-β-羟基酯含量高达99％ee。研究表明，这些配体的吡啶基甲基位置上的额外立体中心对于实现这种氢化作用至关重要。
• Synthesis of N-propionylated (S )-(−)-2-(pyrrolidin-2-yl)propan-2-ol and its use as a chiral auxiliary and selectivity marker in asymmetric aldol reactions
  作者：Erik Hedenström、Fredrik Andersson、Mats Hjalmarsson

  DOI：10.1039/b001730m

  日期：——

  The N-propionylated pyrrolidine derivative and chiral auxiliary, (S)-(−)-2-(pyrrolidin-2-yl)propan-2-ol, was synthesised and used in stereoselective aldol reactions with benzaldehyde. Differences in stereoselectivity were investigated as a function of temperature, solvent, chelating agent and the amount of the chelating agent used by monitoring the 1H NMR spectra of the aldol adducts that were obtained. Among the additives that were investigated, Cp2ZrCl2 induced higher anti-selectivity, while SnCl2 induced higher syn-selectivity respectively. TMSCl was found to induce high selectivity for one syn- and one anti-diastereomer. Varying the ligand sets on titanium additives was found to induce differences in selectivity, with (i-PrO)3TiCl exhibiting syn-selectivity and Cp2TiCl2 exhibiting anti-selectivity. Differences in reactivity and stereoselectivity were also found to depend upon the amount of Lewis acid that was added. Methods for removal of the auxiliary were also investigated. Acidic hydrolysis was used successfully to obtain the desired 3-hydroxy-2-methyl-3-phenylpropionic acids, but was found to give low yields and resulted in a large amount of epimerisation. Furthermore, the ethyl esters of these hydroxy acids are easy to separate into pure syn- and anti-diastereomers by LC.

  合成了N-丙酰化吡咯烷衍生物和手性辅助剂(S)-(β-)-2-(吡咯烷-2-基)丙醇-2，并在与苯甲醛的立体选择性醛醇反应中使用。通过监测获得的醛醇加合物的¹H NMR光谱，研究了立体选择性在温度、溶剂、螯合剂及使用的螯合剂量上的差异。研究的添加剂中，Cp₂ZrCl₂诱导了更高的反式选择性，而SnCl₂则诱导了更高的顺式选择性。发现TMSCl在高选择性上对一个顺式和一个反式二叠体具有影响。改变钛添加剂的配体组合被发现会导致选择性的差异，其中(i-PrO)₃TiCl表现出顺式选择性，而Cp₂TiCl₂则表现出反式选择性。反应性和立体选择性的差异也发现依赖于所添加的路易斯酸的量。还研究了去除辅助剂的方法。酸水解成功用于获得所需的3-羟基-2-甲基-3-苯基丙酸，但发现产率较低，并导致大量的异构化。此外，这些羟基酸的乙基酯可以通过液相色谱轻易分离为纯的顺式和反式二叠体。
• Asymmetric and ?anti?-Selective Aldolisations of Acetates and Propionates. Preliminary Communication
  作者：Wolfgang Oppolzer、Jos� Marco-Contelles

  DOI：10.1002/hlca.19860690725

  日期：1986.10.29

  Starting from acetates 1 and propionates 6, TiCl4-mediated addition of their silyketene acetals 2 and 7 to aldehydes gave aldols 4 and 9, respectively, with high π-face and ‘anti’ differentiation (Schemes, and Tables 1 and 2). Alternation of the (E/Z)-enolate geometry led to reversed α- and β-inductions (7 9b, 8 10b). Non-destructive removal of the auxiliary yielded enantiomerically pure β -hydroxycarboxylic

  从乙酸盐1和丙酸酯6开始，TiCl 4介导的将它们的硅酮烯醇缩醛2和7加到醛中，分别得到具有高π面和'抗'区分性的醇醛4和9（方案，以及表1和表2）。（E / Z）烯醇几何形状的交替导致相反的α和β诱导（7 9b，8 10b）。非破坏性去除辅助生成的对映体纯的β-羟基羧酸13 。