trans-1,2,3,4-tetrahydronaphthalene-1,4-diol | 3344-42-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: trans-1,2,3,4-tetrahydronaphthalene-1,4-diol
• 英文别名: dl-1,2,3,4-tetrahydronaphthalene-1,4-diol；trans-1,4-Dihydroxy-1,2,3,4-tetrahydro-naphthalin；1,4-Dihydroxy-1,2,3,4-tetrahydronaphthalin；(1R,4R)-1,2,3,4-tetrahydronaphthalene-1,4-diol
• CAS: 3344-42-1；19070-56-5；50987-68-3
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: FTCMTZXWNUAYHT-NXEZZACHSA-N

物化性质

• 熔点：
  137.8-138 °C
• 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：

  trans-1,2,3,4-tetrahydronaphthalene-1,4-diol 在 sodium hydroxide 作用下， 以 甲苯 为溶剂， 生成 dl-1,2,3,4-tetrahydronaphthalene-1,4-diol
  参考文献：
  名称：

  Asymmetric Acylation of sec-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center

  摘要：

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.

  DOI：

  10.1021/jo990892p
• 作为产物：
  描述：

  1,4-萘醌 在 CuCr₂O₄ 氢气 作用下， 以 乙醇 为溶剂， 150.0 ℃ 、25.51 MPa 条件下， 生成 trans-1,2,3,4-tetrahydronaphthalene-1,4-diol
  参考文献：
  名称：

  亚铬酸铜催化剂加氢1,4-萘醌和2-甲基-1,4-萘醌

  摘要：

  使用亚铬酸铜催化剂对1,4-萘醌（I）进行加氢可生成新产品反式-1,4-二羟基-1,2,3,4-四氢萘（III）。类似地，2-甲基-1,4-萘醌（IV）得到两个异构的1,4-二羟基-2-甲基-1,2,3,4-四氢萘（VII和VIII），其中羟基是反式的。在升高的温度下，醌IV还会产生两个ac-2-甲基四醇。

  DOI：

  10.1016/s0040-4020(01)98333-4

文献信息

• Asymmetric Synthesis of Bicyclic Diol Derivatives through Metal and Enzyme Catalysis: Application to the Formal Synthesis of Sertraline
  作者：Patrik Krumlinde、Krisztián Bogár、Jan-E. Bäckvall

  DOI：10.1002/chem.200903114

  日期：2010.4.6

  Enzyme‐ and ruthenium‐catalyzed dynamic kinetic asymmetric transformation (DYKAT) of bicyclic diols to their diacetates was highly enantio‐ and diastereoselective to give the corresponding diacetates in high yield with high enantioselectivity (99.9 % ee). The enantiomerically pure diols are accessible by simple hydrolysis (NaOH, MeOH), but an alternative enzyme‐catalyzed ester cleavage was also used

  酶和钌催化的双环二醇向其双乙酸酯的动态动力学不对称转化（DYKAT）具有很高的对映和非对映选择性，从而以高收率和高对映选择性（99.9％ee）得到相应的双乙酸酯 。对映体纯的二醇可通过简单的水解（NaOH，MeOH）进行水解，但是还使用了另一种酶催化的酯裂解方法，以极高的非对映异构体纯度得到反式二醇（R，R）-1 b（反式/顺式= 99.9：0.1，> 99.9％  ee）。结果表明，在钌催化的Oppenauer型反应中，二醇可以选择性地氧化为酮醇。从简单的外消旋的顺式/反式二醇1b证实了舍曲林的形式对映体选择性合成。
• Tetrahydronaphthalene-1,4-dione and its Chromiumtricarbonyl Complex
  作者：Álvaro Enríquez García、E. Peter Kündig、Thierry Lomberget、Ryan Bragg、Cyril Poulard、Gerald Bernardinelli

  DOI：10.2533/chimia.2007.169

  日期：——

  The article gives a brief outline of the rediscovery of tetrahydronaphthalene-1,4-dione, a stable tautomer which has been known for over half a century but has not been applied in synthesis. Desymmetrization is readily achieved via enantioselective reduction. Synthetic potential apart, the dione and its chromiumtricarbonyl complex are of theoretical interest. Thus, whereas dihydroxynaphthalene requires quite harsh conditions and leads to a 1:1 mixture of the two tautomers, the chromiumtricarbonyl complex of dihydroxynaphthalene tautomerizes under very mild conditions to the tetrahydronaphthalene-1,4-dione complex. An earlier literature report showed that in trifluoroacetic acid, the dione tautomer is present exclusively. This has now been used to isolate multigram quantities of the compound.

  这篇文章简要介绍了四氢萘-1,4-二酮的重新发现，这是一种稳定的互变异构体，已知已有半个世纪，但尚未应用于合成。通过对映选择性还原，可以轻松实现非对称化。除了合成潜力外，这种二酮及其铬三羰基配合物也具有理论兴趣。因此，虽然二氢萘酚需要相当严酷的条件，并导致两种互变异构体的1:1混合物，但二氢萘酚的铬三羰基配合物在非常温和的条件下发生互变异构，形成四氢萘-1,4-二酮配合物。早期的文献报告表明，在三氟乙酸中，只存在二酮互变异构体。现在已经利用这一点来分离多克量的化合物。
• New Synthetic Inhibitors of Fatty Acid Synthase with Anticancer Activity
  作者：Carlos Turrado、Teresa Puig、Javier García-Cárceles、Marta Artola、Bellinda Benhamú、Silvia Ortega-Gutiérrez、Joana Relat、Gloria Oliveras、Adriana Blancafort、Diego Haro、Pedro F. Marrero、Ramón Colomer、María L. López-Rodríguez

  DOI：10.1021/jm2016045

  日期：2012.6.14

  Fatty acid synthase (FASN) is a lipogenic enzyme that is highly expressed in different human cancers. Here we report the development of a new series of polyphenolic compounds 5-30 that have been evaluated for their cytotoxic capacity in SK-Br3 cells, a human breast cancer cell line with high FASN expression. The compounds with art IC50 < 50 mu M have been tested for their ability to inhibit FASN activity. Among them, derivative 30 blocks the 90% of FASN activity at low concentration (4 mu M), is highly cytotoxic in a broad panel of tumor cells, induces apoptosis, and blocks the activation of HER2, AKT, and ERK pathways. Remarkably, 30 does not activate carnitine palmitoyltransferase-1 (CPT-1) nor induces in mice weight loss, which are the main drawbacks of other previously described FASN inhibitors. Thus, FASN inhibitor 30 may aid the validation of this enzyme as a therapeutic target for the treatment of cancer.
• Rediscovery, Isolation, and Asymmetric Reduction of 1,2,3,4-Tetrahydronaphthalene-1,4-dione and Studies of Its [Cr(CO)3] Complex
  作者：E. Peter Kündig、Alvaro Enríquez García、Thierry Lomberget、Gérald Bernardinelli

  DOI：10.1002/anie.200502588

  日期：2006.1
• Asymmetric Acylation of <i>s</i><i>ec</i>-Alcohols with Twisted Amides Possessing Axial Chirality Induced by the Adjacent Asymmetric Center
  作者：Shinji Yamada、Hiroko Katsumata

  DOI：10.1021/jo990892p

  日期：1999.12.1

  This paper reports that axially chiral twisted amides serve as asymmetric acylating agents for sec-alcohols under neutral conditions. Kinetic resolution of various racemic sec-alcohols and desymmetrization of 1,2-, 1,3-, and 1,4-meso-diols were performed by using the twisted amides. The utility of this desymmetrization method was shown by the preparation of the synthetic intermediate 28 for macrolide antibiotic nodusmicin and 18-deoxynargenicin. The stereoselectivity of the acylation reactions is significantly dependent on the bulkiness of both the acyl group and the C-4 substituent of the chiral auxiliary. When an amide possessing an imidazolyl group at C-4 was employed, the stereoselectivity was reversed to give R esters. A possible working model of the acylation reaction is also described on the basis of the structural studies of the twisted amides by IR and H-1 and C-13 NMR spectroscopies and AM1 calculations. These studies suggested that rotamer II is thermodynamically more stable than the others. The rotamer II has an axial chirality about its C(O)-N linkage that is induced by the adjacent chiral center. This would enable discrimination of the two enantiomeric hydroxy groups of the racemic alcohols or meso-diols.