meso-p-bis(1-hydroxyethyl)benzene | 112710-41-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: meso-p-bis(1-hydroxyethyl)benzene
• 英文别名: (R,S)-α,α'-dimethyl-1,4-benzenedimethanol；meso-α,α'-dihydroxy-1,4-diethylbenzene；meso-α,α’-dimethyl-(1,4-benzene)dimethanol；(1R)-1-[4-[(1S)-1-hydroxyethyl]phenyl]ethanol
• CAS: 112710-41-5
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: BHCGGVIVFXWATI-OCAPTIKFSA-N

物化性质

• 沸点：
  297.1±20.0 °C(Predicted)
• 密度：
  1.096±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  meso-p-bis(1-hydroxyethyl)benzene 在 (S)-(4-tert-butyl-2-thioxooxazolidin-3-yl)[4-(dimethylamino)pyridin-3-yl]methanone 、 sodium hydroxide 、 甲基叔丁基醚 、 戴斯-马丁氧化剂 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 1-{4-[(1R)-1-羟基乙基]苯基}乙酮
  参考文献：
  名称：

  吡啶催化剂的新类别，它具有一个构象开关系统：不同的不对称酰化小号EC -醇

  摘要：

  我们已经开发了用于具有构象转换系统的仲醇的不对称酰化的新型吡啶催化剂，在该构象转换系统中，分别通过酰化和脱酰步骤引起自复合和非复合之间的相互转化。各种仲醇的动力学拆分通过异丁酸酐的不对称酰化反应使用0.05至0.5 mol％的催化剂1a（s值最高为30）进行。此外，dl-二醇也以相似的方式以良好的选择性拆分。此外，在存在0.5-5 mol％催化剂的情况下，内消旋-1，X-二醇（X = 2-6）不对称脱对称1a。在1 H NMR测量，X射线结构分析以及AM1和DFT计算的基础上，提出了反应机理的工作模型，其中构象转换系统由吡啶环与环之间的分子内阳离子-π相互作用控制。硫羰基将在获得良好的选择性和高催化活性方面起关键作用。

  DOI：

  10.1021/jo060989t
• 作为产物：
  描述：

  1-[4-(1-羟乙基)苯基]乙醇 在 amano lipase PS C₁ 、 potassium hydroxide 作用下， 以 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 38.0h， 生成 meso-p-bis(1-hydroxyethyl)benzene
  参考文献：
  名称：

  Aerobic oxidative desymmetrization of meso-diols with bifunctional amidoiridium catalysts bearing chiral N-sulfonyldiamine ligands

  摘要：

  Asymmetric aerobic oxidation of a range of meso- and prochiral diols with chiral bifunctional Ir catalysts is described. A high level of chiral discrimination ability of Cp*Ir complexes derived from (S,S)-1,2-diphenylethylenediamine was successfully demonstrated by desymmetrization of secondary benzylic diols such as cis-indan-1,3-diol and cis-1,4-diphenylbutane-1,4-diol, providing the corresponding (R)-hydroxyl ketones with excellent chemo- and enantioselectivities. Enantiotopic group discrimination in oxidation of symmetrical primary 1,4- and 1,5-diols gave rise to chiral lactones with moderate ees under similar aerobic conditions. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.12.103

文献信息

• Combined Ruthenium(II) and Lipase Catalysis for Efficient Dynamic Kinetic Resolution of Secondary Alcohols. Insight into the Racemization Mechanism
  作者：Belén Martín-Matute、Michaela Edin、Krisztián Bogár、F. Betül Kaynak、Jan-E. Bäckvall

  DOI：10.1021/ja051576x

  日期：2005.6.1

  Pentaphenylcyclopentadienyl ruthenium complexes (3) are excellent catalysts for the racemization of secondary alcohols at ambient temperature. The combination of this process with enzymatic resolution of the alcohols results in a highly efficient synthesis of enantiomerically pure acetates at room temperature with short reaction times for most substrates. This new reaction was applied to a wide range

  五苯基环戊二烯基钌配合物 (3) 是室温下仲醇外消旋化的极好催化剂。该过程与醇的酶促拆分相结合，可以在室温下高效合成对映异构纯的乙酸酯，大多数底​​物的反应时间都很短。这种新反应适用于包括杂芳族醇在内的多种官能化醇，对于后者中的许多醇，首次通过动态动力学拆分 (DKR) 有效制备了对映纯乙酸酯。制备并研究了不同取代的环戊二烯基钌配合物作为醇外消旋化的催化剂。发现五芳基取代的环戊二烯基配合物是外消旋化的高效催化剂。用烷基取代芳基之一大大减慢了外消旋化过程。氢化钌 eta(5)-Ph(5)CpRu(CO)(2)H (8) 催化 (S)-1-苯基乙醇外消旋化的研究表明外消旋化发生在钌的配位范围内催化剂。在对甲苯基甲基酮（1 当量）存在下进行的 (S)-1-苯基乙醇外消旋化中缺乏酮交换支持这一结论，这产生 <1% 的 1-(对甲苯基)乙醇. 氯化钌和碘化物配合物 3a 和 3c 以及氢化钌配合物 8
• Dynamic Kinetic Resolution of Secondary Diols via Coupled Ruthenium and Enzyme Catalysis
  作者：B. Anders Persson、Fernando F. Huerta、Jan-E. Bäckvall

  DOI：10.1021/jo990447u

  日期：1999.7.1

  Enzymatic acylation of secondary symmetrical diols (as meso/dl mixtures) in combination with ruthenium-catalyzed isomerization of the diol led to efficient dynamic kinetic resolution. In this way, a meso/dl mixture of the diol was transformed to enantiomerically pure (R,R)-diacetate, making efficient use of all the diol material. For some of the flexible substrates, substantial amounts of meso-diacetates

  二级对称二醇的酶促酰化（作为 meso/dl 混合物）与钌催化的二醇异构化相结合，导致有效的动态动力学拆分。通过这种方式，二醇的内消旋/dl 混合物转化为对映异构纯的 (R,R)-二乙酸酯，从而有效利用所有二醇材料。对于一些柔性基材，大量的内消旋二乙酸盐作为副产物形成。结果表明，内消旋产物的主要部分是通过分子内酰基转移途径形成的。
• Process for the preparation of an optically active ester
  申请人：DSM IP Assets B.V.

  公开号：EP1710221A1

  公开（公告）日：2006-10-11

  The invention relates to a process for the preparation of an optically active compound from raw materials comprising a di-ester and a chiral hydroxy-compound according to formula (I): wherein: - R1, R2, R4 and R5 each independently represent hydrogen or an alkyl group with 1-20 C-atoms, an alkenyl group with 2-20 C-atoms, an alkynyl group with 2-20 C-atoms,or an (hetero)aryl group with 4-20 C-atoms optionally containing one or more O, S or N atoms, - R3 represents an alkyl group with 1-20 C-atoms, an alkenyl group with 2-20 C-atoms, an alkynyl group with 2-20 C-atoms, or an (hetero)aryl group with 4-20 C-atoms optionally containing one or more O, S or N atoms, - the compound according to formula (I) comprises at least one chiral centre that has an α-carbon relative to a secondary hydroxy group, comprising the steps of a) bringing the di-ester, optionally a solvent, and the chiral hydroxy-compound according to formula (I) together to form a reaction system; b) adding an asymmetric transesterification catalyst, a racemisation catalyst and optionally a racemisation catalyst re-activating compound to the reaction system; c) bringing the reaction system to conditions where racemisation and enantioselective transesterefication take place, whereby the optically active compound is formed, whereby steps a), b) and c) may be executed sequentially or simultaneously, and whereby the chiral hydroxy-compound according to formula (I) may in step a) be partially or wholly replaced by the combination of the corresponding ketone and a reducing agent.

  该发明涉及一种从原料制备手性活性化合物的过程，所述原料包括一种二酯和一种手性羟基化合物，其化学式为（I）： 其中： - R1、R2、R4和R5分别独立地代表氢或具有1-20个碳原子的烷基基团，具有2-20个碳原子的烯基基团，具有2-20个碳原子的炔基基团，或者具有4-20个碳原子的（杂）芳基团，可选地含有一个或多个O、S或N原子； - R3代表具有1-20个碳原子的烷基基团，具有2-20个碳原子的烯基基团，具有2-20个碳原子的炔基基团，或者具有4-20个碳原子的（杂）芳基团，可选地含有一个或多个O、S或N原子； - 化合物按照化学式（I）至少包含一个手性中心，该手性中心具有相对于次级羟基的α-碳，包括以下步骤： a）将二酯、可选的溶剂和按照化学式（I）的手性羟基化合物置于一起形成反应体系； b）向反应体系中加入不对称的酯交换催化剂、消旋催化剂和可选的消旋催化剂再活化化合物； c）将反应体系带到使消旋和对映选择性酯交换发生的条件下，从而形成手性活性化合物； 其中步骤a）、b）和c）可以顺序执行或同时执行，且化学式（I）的手性羟基化合物在步骤a）中可以部分或完全被相应的酮和还原剂的组合所替代。
• Practical Enantioselective Hydrogenation of Aromatic Ketones
  作者：Takeshi Ohkuma、Hirohito Ooka、Shohei Hashiguchi、Takao Ikariya、Ryoji Noyori

  DOI：10.1021/ja00114a043

  日期：1995.3
• Separation of remote diol and triol stereoisomers by enzyme-catalyzed esterification in organic media or hydrolysis in aqueous media
  作者：J. Shield Wallace、Bruce W. Baldwin、Cary Morrow

  DOI：10.1021/jo00045a042

  日期：1992.9

  The separation of symmetric, remote, secondary diol stereoisomers by steroselective enzyme-catalyzed acetylation with acetic anhydride in anhydrous, low polarity organic solvents or by stereoselective enzyme-catalyzed hydrolysis of the corresponding peracetate in aqueous media is described. Whether or not an alcohol is acetylated or an acetate is hydrolyzed is determined solely by its own stereochemical arrangement and not by the stereochemistry at any other stereogenic center. Since the enzyme used, Amano P lipoprotein lipase from Pseudomonas species, acetylates secondary alcohol stereogenic centers of the (R)-configuration, an (R,R)-diol is converted to its diacetate, a meso-diol is converted to the monoacetate at its (R)-stereogenic center, and an (S,S)-diol is left unchanged. Similarly, when hydrolysis is used, (R)-stereogenic centers are hydrolyzed so that the (R,R)-stereoisomer is converted to the corresponding diol while the (S,S)-stereoisomer remains a diacetate. The resulting mixture is separated, and the remaining acetates are removed by hydrolysis to give diols and triols of high stereochemical purity. Diols successively separated by esterification include alpha,alpha-dimethyl-1,4-benzenedimethanol, 1, alpha,alpha'-dimethyl-1,3-benzenedimethanol, 4, alpha,alpha'-dimethyl-2,6-pyridinedimethanol, 5, and alpha,alpha-dimethyl-4,4-biphenylenedimethanol, 6. For two cases, alpha,alpha'-dimethyl-2,6-pyridinedimethanol, 5, and alpha,alpha',alpha''-trimethyl-1,3,5-benzenetrimethanol, 7, the separation was achieved using the hydrolysis procedure. The stereochemical purity of each of the separated diol stereoisomers was determined by evaluating the NMR spectrum of its bis-MTPA ester. In most cases, it was possible to establish both the stereochemical purity of the fraction and the amount of each contaminating stereoisomer that was present. The diol products are expected to be of value for preparing optically active polymers and optically active crown ethers.