(1R,2R)-反式-1,2,3,4-四氢-1,2-萘二醇 | 57496-61-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 中文名称: (1R,2R)-反式-1,2,3,4-四氢-1,2-萘二醇
• 英文名称: (1R,2R)-trans-1,2-dihydroxy-1,2,3,4-tetrahydronaphthalene
• 英文别名: (1R,2R)-1,2,3,4-tetrahydronaphthalene-1,2-diol；(R,R)-1,2-dihydroxy-1,2,3,4-terahydronaphthalene；(1R,2R)-1,2-dihydroxy-1,2,3,4-tetrahydronaphthalene；1(e),2(e)-Dihydroxy-tetralin；(1R)-trans-1,2,3,4-tetrahydro-naphthalene-1,2-diol；(1R)-trans-1,2,3,4-Tetrahydro-naphthalin-1,2-diol
• CAS: 57496-61-4
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: KMQJJAOZMONGLS-NXEZZACHSA-N

物化性质

• 熔点：
  114-115 °C
• 沸点：
  308.4±42.0 °C(Predicted)
• 密度：
  1.260±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 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：

  (1R,2R)-反式-1,2,3,4-四氢-1,2-萘二醇 在 2,3-butanediol dehydrogenase-lactate dehydrogenase from Bacillus subtilis 作用下， 以 aq. buffer 为溶剂， 反应 4.0h， 生成 (R)-(+)-2-hydroxy-3,4-dihydro-2H-naphthalen-1-one
  参考文献：
  名称：

  外消旋反式环状邻苯二酚的对映选择性生物氧化：对映纯（S，S）-环状邻苯二酚和（R）-α-羟基酮的一锅合成

  摘要：

  AbstractHighly regio‐ and enantioselective alcohol dehydrogenases BDHA (2,3‐butanediol dehydrogenase from Bacillus subtilis BGSC1A1), CDDHPm (cyclic diol dehydrogenase from Pseudomonas medocina TA5), and CDDHRh (cyclic diol dehydrogenase from Rhodococcus sp. Moj‐3449) were discovered for the oxidation of racemic trans‐cyclic vicinal diols. Recombinant Escherichia coli expressing BDHA was engineered as an efficient whole‐cell biocatalyst for the oxidation of (±)‐1,2‐cyclopentanediol, 1,2‐cyclohexanediol, 1,2‐cycloheptane‐diol, and 1,2‐cyclooctanediol, respectively, to give the corresponding (R)‐α‐hydroxy ketones in >99% ee and (S,S)‐cyclic diols in >99% ee at 50% conversion in one pot. Escherichia coli (BDHA‐LDH) co‐expressing lactate dehydrogenase (LDH) for intracellular regeneration of NAD+ catalyzed the regio‐ and enantioselective oxidation of (±)‐1,2‐dihydroxy‐1,2,3,4‐tetrahydronaphthalene to produce the corresponding (R)‐α‐hydroxy ketone in >99% ee and (S,S)‐cyclic diol in 96% ee at 49% conversion. Preparative biotransformations were also demonstrated. Thus, a novel and useful method for the one‐pot synthesis of both vicinal diols and α‐hydroxy ketones in high ee was developed via highly regio‐ and enantioselective oxidations of the racemic vicinal diols.magnified image

  DOI：

  10.1002/adsc.201300301
• 作为产物：
  描述：

  1,2,3,4-四氢-1-萘酚 在 sodium hypochlorite 、 disodium hydrogenphosphate 、 Jacobsen's catalyst 、 camphor-10-sulfonic acid 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 水 、 丙酮 、 甲苯 为溶剂， 反应 21.0h， 生成 (1R,2R)-反式-1,2,3,4-四氢-1,2-萘二醇
  参考文献：
  名称：

  Verification of the Major Metabolic Oxidation Path for the Naphthoyl Group in Chemoattractant Receptor-Homologous Molecule Expressed on Th2 Cells (CRTh2) Antagonist 2-(2-(1-Naphthoyl)-8-fluoro-3,4-dihydro-1H-pyrido[4,3-b]indol-5(2H)-yl)acetic Acid (Setipiprant/ACT-129968)

  摘要：

  Various racemic and enantioenriched (trans)-X,Y-dihydroxy-X,Y-dihydronaphthoyl analogues as well as X-hydroxy-naphthoyl analogues of CRTh2 antagonist 2-(2-(1-naphthoyl)-8-fluoro-3,4-dihydro-1H-pyrido [4,3-b]indol-5(2H)-yl) acetic acid (1, Setipiprant/ACT-129968) were synthesized in order to gain insight into regio- and enantioselectivity of the metabolic oxidation of 1 and to verify the structures of four metabolites that were proposed earlier in a clinical ADME study. Analytical data of the synthetic standards were compared with data from samples of biological origin. The two major metabolites M7 and M9 were unambiguously verified as 2-(2-((trans)-3,4-dihydroxy-3,4-dihydronaphthalene-1-carbony1)- and 242-((trans)-5,6-dihydroxy-5,6-dihydronaphthalene-1-carbonyl)-8-fluoro-3,4-dihydro-1H-pyrido [4,3-b]indol-5 (2H)-yl) acetic acid, respectively, each composed of two enantiomers with 68% and 44% ee in favor of (+)-(3S,4S)-M7 and (+)-(5S,6S)-M9, respectively. Likewise, minor metabolites M3 and M13 were identified as 2-(8-fluoro-2-(5-hydroxy-1-naphthoyl) and 2-(8-fluoro-2-(4-hydroxy-1-naphthoyl)-1,2,3,4-tetrahydro-5H-pyrido[4,3-b]indol-5-yl)acetic acid, respectively.

  DOI：

  10.1021/acs.jmedchem.5b00824

文献信息

• Microbiological transformation 32: Use of epoxide hydrolase mediated biohydrolysis as a way to enantiopure epoxides and vicinal diols: Application to substituted styrene oxide derivatives
  作者：S Pedragosa-Moreau、A Archelas、R Furstoss

  DOI：10.1016/0040-4020(96)00135-4

  日期：1996.3

  The biohydrolyses of various substituted styrene oxide derivatives using the fungi Aspergillus niger or Beauveria sulfurescens are described. The results obtained show that this methodology allows the preparation of enantiomerically enriched epoxides and diols via enantioselective and regioselective hydration. The comparative study of the results obtained suggests that these hydrolyses operate following

  描述了使用真菌黑曲霉或硫白僵菌的各种取代的苯乙烯氧化物衍生物的生物水解。获得的结果表明，该方法可以通过对映选择性和区域选择性水合制备对映体富集的环氧化物和二醇。对所得结果的比较研究表明，这些水解遵循不同的机理，并提出了相应活性位点的模型。
• Enantioselective trans-Dihydroxylation of Aryl Olefins by Cascade Biocatalysis with Recombinant <i>Escherichia coli</i> Coexpressing Monooxygenase and Epoxide Hydrolase
  作者：Shuke Wu、Yongzheng Chen、Yi Xu、Aitao Li、Qisong Xu、Anton Glieder、Zhi Li

  DOI：10.1021/cs400992z

  日期：2014.2.7

  85–89% for 5 diols; 65% for 1 diol). E. coli (SSP1) and E. coli (SST1) catalyzed the trans-dihydroxylation of trans-aryl olefin 16a and cis-aryl olefin 17a with excellent and complementary stereoselectivity, giving each of the four stereoisomers of 1-phenyl-1,2-propanediol 16c in high ee and de, respectively. Both strains catalyzed the trans-dihydroxylation of aryl cyclic olefins 18a and 19a to afford

  通过细胞内环氧化和水解的级联生物催化被开发为一种绿色高效的方法，用于芳基烯烃的对映选择性二羟基化，以高ee和高收率制备手性邻位二醇。共表达苯乙烯单加氧酶（SMO）和环氧化物水解酶SPEH的大肠杆菌（SSP1）是一种简单有效的生物催化剂，用于末端芳基烯烃1a - 15a的S-对映选择性二羟基化，得到（S）-邻位二醇1c - 15c高ee（10二醇为97.5–98.6％； 3二醇为92.2–93.9％）和高收率（6二醇为91–99％； 2二醇为86–88％； 3二醇为67％）。将SMO和环氧化物水解酶STEH组合起来对SPEH作为级联生物催化的生物催化剂具有互补的区域选择性，从而产生芳基烯烃的R-对映选择性二羟基化反应，这是这种方法逆转了级联生物催化整体对映选择性的第一个例子。共表达SMO和STEH的大肠杆菌（SST1）也被设计为绿色和高效的生物催化剂，用于末端芳基烯烃1a - 15a的R-二羟基化，得到（R）-邻二醇1c
• Production Of Enantiopure alpha-Hydroxy Carboxylic Acids From Alkenes By Cascade Biocatalysis
  申请人：NATIONAL UNIVERSITY OF SINGAPORE

  公开号：US20160097063A1

  公开（公告）日：2016-04-07

  The invention provides compositions comprising an alkene epoxidase and a selective epoxide hydrolase, such as a recombinant microorganism comprising a first heterologous nucleic acid encoding an alkene epoxidase and a second heterologous nucleic acid encoding a selective epoxide hydrolase. Exemplary alkene epoxidases include StyAB, while exemplary selective epoxide hydrolases include epoxide hydrolases from Sphingomonas, Solanum tuberosum , or Aspergillus . The invention also provides non-toxic methods of making enantiomerically pure vicinal diols or enantiomerically pure alpha-hydroxy carboxylic acids using these compositions and microorganisms.

  该发明提供了包含烯烃环氧化酶和选择性环氧水解酶的组合物，例如包括编码烯烃环氧化酶的第一异源核酸和编码选择性环氧水解酶的第二异源核酸的重组微生物。示例烯烃环氧化酶包括StyAB，而示例选择性环氧水解酶包括来自Sphingomonas、Solanum tuberosum或Aspergillus的环氧水解酶。该发明还提供了使用这些组合物和微生物制备对映纯邻二醇或对映纯α-羟基羧酸的无毒方法。
• Stereoselective Amination of Chiral Benzylic Ethers Using Chlorosulfonyl Isocyanate: Total Synthesis of (+)-Sertraline
  作者：Sang Hwi Lee、In Su Kim、Qing Ri Li、Guang Ri Dong、Lak Shin Jeong、Young Hoon Jung

  DOI：10.1021/jo201794k

  日期：2011.12.16

  The stereoselective amination of various chiral benzylic ethers using chlorosulfonyl isocyanate is developed, and the application of this method to the total synthesis of a potent antidepressant, (+)-sertraline, from readily available 1-naphthol is also described.

  已开发出使用氯磺酰基异氰酸酯对各种手性苄基醚进行立体选择性胺化的方法，还描述了该方法在从容易获得的1-萘酚全合成强效抗抑郁药（+）-舍曲林中的应用。
• Enantioselective, Stereoconvergent Resolution Copolymerization of Racemic <i>cis</i> ‐Internal Epoxides and Anhydrides
  作者：Guang‐Hui He、Bai‐Hao Ren、Shi‐Yu Chen、Ye Liu、Xiao‐Bing Lu

  DOI：10.1002/anie.202011259

  日期：2021.3.8

  unreacted epoxide at various conversions. Catalytic activity and copolymer enantioselectivity are strongly influenced by the phenolate ortho‐substituents of the ligand set, as well as the axial linker and its chirality. An enantiopure binaphthol‐linked bimetallic AlIII complex allows stereoconvergent access to the stereoregular semi‐crystalline polyesters and a concomitant kinetic resolution of the

  外消旋的顺式-内部环氧化物和酸酐的前所未有的对映选择性拆分共聚反应，是由具有多个手性的双核铝配合物介导的，提供了具有两个连续立体中心的旋光聚酯，以及未反应的底物具有良好的对映选择性。在该拆分共聚中观察到了意外的立体收敛，其中共聚物的对映选择性形成的选择性因子大大超过了在各种转化率下基于未反应的环氧化物的动力学拆分系数。催化活性和共聚物的对映选择性受配体组的酚酸酯邻位取代基，轴向连接基及其手性的影响很大。对映纯联萘酚双金属Al III 配合物可以使立体收敛地接触到有规立构的半结晶聚酯，并伴随着环氧底物的动力学拆分。

表征谱图