meso-1,2,3,4-tetrahydronaphthalene-1,4-diol | 50987-68-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: meso-1,2,3,4-tetrahydronaphthalene-1,4-diol
• 英文别名: cis-1,2,3,4-tetrahydronaphthalene-1,4-diol；cis-tetrahydronaphthalene-1,4-diol；(1R,4S)-1,2,3,4-tetrahydronaphthalene-1,4-diol (racemic)；(1S,4R)-1,2,3,4-tetrahydronaphthalene-1,4-diol
• CAS: 50987-68-3；661461-05-8
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: FTCMTZXWNUAYHT-AOOOYVTPSA-N

物化性质

• 沸点：
  353.4±30.0 °C(Predicted)
• 密度：
  1.260±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• 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-1,2,3,4-tetrahydronaphthalene-1,4-diol 在 Cp* Ir[(S,S)-Msdpen] 作用下， 以 四氢呋喃 为溶剂， 30.0 ℃ 、101.33 kPa 条件下， 反应 48.0h， 以93%的产率得到(R)-4-hydroxy-3,4-dihydronaphthalene-1(2H)-one
  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
• 作为产物：
  描述：

  1,4-二羟基萘 在 L-Selectride 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙二醇二甲醚 为溶剂， 反应 25.0h， 生成 meso-1,2,3,4-tetrahydronaphthalene-1,4-diol
  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

• The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications
  作者：David C. Ebner、Jeffrey T. Bagdanoff、Eric M. Ferreira、Ryan M. McFadden、Daniel D. Caspi、Raissa M. Trend、Brian M. Stoltz

  DOI：10.1002/chem.200902172

  日期：2009.12.7

  and tert‐butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 °C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good‐to‐excellent

  已经开发出第一个钯催化的仲醇对映选择性氧化反应，利用容易获得的二胺（-）-金雀花石作为手性配体，分子氧作为化学计量氧化剂。关于碱基和氢键供体作用的机制见解导致了对原始系统的一些改进。也就是说，碳酸铯和叔丁醇的添加大大提高了反应速率，促进了快速分辨率。使用氯仿作为溶剂允许在 23 °C 下使用环境空气作为终端氧化剂，从而提高催化剂选择性。这些改进的反应条件使得能够以良好至优异的选择性因子成功地将苄基、烯丙基和环丙基仲醇动力学拆分为高对映体过量。该催化剂体系也已应用于内消旋二醇的去对称化，提供高产率的对映体富集的羟基酮。
• SYNTHESIS AND APPLICATION OF CHIRAL SUBSTITUTED POLYVINYLPYRROLIDINONES
  申请人：Kansas State University Research Foundation

  公开号：US20200306737A1

  公开（公告）日：2020-10-01

  Chiral polyvinylpyrrolidinone (CSPVP), complexes of CSPVP with a core species, such as a metallic nanocluster catalyst, and enantioselective oxidation reactions utilizing such complexes are disclosed. The CSPVP complexes can be used in asymmetric oxidation of diols, enantioselective oxidation of alkenes, and carbon-carbon bond forming reactions, for example. The CSPVP can also be complexed with biomolecules such as proteins, DNA, and RNA, and used as nanocarriers for siRNA or dsRNA delivery.

  手性聚乙烯吡咯烷酮（CSPVP），CSPVP与金属纳米团簇催化剂等核心物种形成的络合物，以及利用这种络合物进行对映选择氧化反应的方法被揭示。CSPVP络合物可用于不对称二醇氧化、烯烃对映选择氧化以及碳-碳键形成反应等。CSPVP还可以与蛋白质、DNA和RNA等生物分子形成络合物，并用作siRNA或dsRNA传递的纳米载体。
• Catalytic Asymmetric Desymmetrization of Cyclic <i>m</i><i>eso</i>-1,3- and 1,4-Diols by a Phosphinite Derivative of Quinidine
  作者：Shinya Mizuta、Takeo Tsuzuki、Tetsuya Fujimoto、Iwao Yamamoto

  DOI：10.1021/ol051129m

  日期：2005.8.1

  Asymmetric monobenzoylation reactions of cyclic meso-1,3- and 1,4-diols were catalyzed by a phosphinite derivative of quinidine to afford the corresponding monobenzoylated diol with good yield and enantioselectivity. [reaction: see text]

  奎尼丁的次膦酸酯衍生物催化环状1,3-和1,4-二醇的不对称单苯甲酰化反应，从而以良好的收率和对映选择性提供相应的单苯甲酰化二醇。[反应：看文字]
• The Palladium-Catalyzed Oxidative Kinetic Resolution of Secondary Alcohols with Molecular Oxygen
  作者：Eric M. Ferreira、Brian M. Stoltz

  DOI：10.1021/ja015791z

  日期：2001.8.1

  The oxidation of secondary alcohols is one of the most common and well-studied reactions in chemistry. Although excellent catalytic enantioselective methods exist for a variety of oxidation processes, such as epoxidation, dihydroxylation, and aziridination, it is surprising that there are relatively few catalytic enantioselective examples of the ubiquitous alcohol oxidation. In connection with a general

  仲醇的氧化是化学中最常见和研究最充分的反应之一。尽管对于各种氧化过程（例如环氧化、二羟基化和氮丙啶化）存在出色的催化对映选择性方法，但令人惊讶的是，无处不在的醇氧化的催化对映选择性实例相对较少。结合处理新催化氧化系统发现的一般程序，我们在此介绍了使用分子氧作为末端氧化剂的仲醇催化氧化动力学拆分的开发（参见方案 1）。
• New Class of Pyridine Catalyst Having a Conformation Switch System:  Asymmetric Acylation of Various <i>s</i><i>ec</i>-Alcohols
  作者：Shinji Yamada、Tomoko Misono、Yuko Iwai、Ayako Masumizu、Yukiko Akiyama

  DOI：10.1021/jo060989t

  日期：2006.9.1

  new class of pyridine catalyst for asymmetric acylation of sec-alcohols having a conformation switch system in which interconversion between self-complexation and uncomplexation is induced by acylation and deacylation steps, respectively. Kinetic resolution of various sec-alcohols is performed by the asymmetric acylation with isobutyric anhydride using 0.05 to 0.5 mol % catalyst 1a with s values of up

  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。