Methyl 2,2'-dihydroxy-1,1'-binaphthalene-3-carboxylate | 145415-63-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: Methyl 2,2'-dihydroxy-1,1'-binaphthalene-3-carboxylate
• 英文别名: methyl 3-hydroxy-4-(2-hydroxynaphthalen-1-yl)naphthalene-2-carboxylate
• CAS: 145415-63-0
• 化学式: C₂₂H₁₆O₄
• 分子量: 344.367
• InChiKey: NQWPVDNYXWMQGJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 2,2'-dihydroxy-1,1'-binaphthalene-3-carboxylate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 3,3'-hydroxylmethyl-1,1'-binaphthalene
  参考文献：
  名称：

  Studies on apoptosis in HeLa cells via the ROS-mediated mitochondrial pathway induced by new dibenzoxanthenes

  摘要：

  二苯并氧蒽类化合物C1和C2的凋亡机制被发现是ROS介导的内源性线粒体-caspase蛋白酶的激活。

  DOI：

  10.1039/c6nj00250a
• 作为产物：
  描述：

  (+/-)-methyl 7'-bromo-2,2'-dihydroxy-1,1'-binaphthalene-3-carboxylate 在 盐酸 、 sodium hydroxide 、 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 31.25h， 生成 Methyl 2,2'-dihydroxy-1,1'-binaphthalene-3-carboxylate
  参考文献：
  名称：

  Asymmetric Phase-Transfer Catalysis by Quaternary Ammonium Ions Derived fromCinchona-Alkaloid Analogs Containing 1,1′-Binaphthalene Moieties

  摘要：

  The synthesis and catalytic properties of a new type of enantioselective phase-transfer catalysts, incorporating both the quinuclidinemethanol fragment of Cinchona alkaloids and a 1,1'-binaphthalene moiety, are described. Catalyst (+)-(aS,3R,4S,8R,9S)-4 with the quinuclidine fragment attached to C(7') in the major groove of the 1,1'-binaphthalene residue was predicted by computer modeling to be an efficient enantioselective catalyst for the unsymmetric alkylation of 6,7-dichloro-5-methoxy-2-phenylindanone (1; Scheme I, Fig. I). Its synthesis involved the selective oxidative cross-coupling of two differently substituted naphthalen-2-ols to afford the asymmetrically substituted 1,1'-binaphthalene derivative (+/-)-17 in high yield (Scheme 3). Chromatographic optical resolution via formation of diastereoisomeric camphorsulfonyl esters and functional-group manipulation gave access to the 7-bromo-1,1'-binaphthalene derivative (-)-(aS)-11 (Scheme 4). Nucleophilic addition of lithiated (-)-(aS)-11 to the quinuclidine Weinreb amide (+)-(3R,4S,8R)-8 afforded the two ketones (aS,3R,4S,8R)-27 and (aS,3R,4S,8S)-28 as an inseparable mixture of diastereoisomers (Scheme 6). Stereoselective reduction of this mixture with DIBAL-H (diisobutylaluminum hydride; preferred formation of the C(8)-C(9) erythro-pair of diastereoisomers with 18% de) or with NaBH4 (preferred formation of the threo-pair of diastereoisomers with 50% de) afforded the four separable diastereoisomers (+)-(aS,3R,4S,8S,9S)-29, (+)-(aS,3R,4S,8R,9R)-30, (-)-(aS,3R,4S,8S,9R)-31, and (+)-(aS,3R,4S,8R,9S)-32 (Scheme 6). A detailed conformational analysis, combining H-1-NMR spectroscopy and molecular-mechanics computations, revealed that the four diastereoisomers displayed distinctly different conformational preferences (Figs. 2 and 3). These novel Cinchona-alkaloid analogs were quaternized to give (+)-(aS,3R,4S,8R,9S)-4, (+)-(aS,3R,4S,8S,9S)-5, (+)(aS,3R,4S,8R,9R)-6, and (-)-(aS,3R,4S,8S,9R)-7 (Scheme 7) which were tested as phase-transfer agents in the asymmetric allylation of phenylindanone 1. Without any optimization work, (+)-(aS,3R,4S,8R,9S)-4 was found to catalyze the allylation of 1 yielding the predicted enantiomer (+)-(S)-3b in 32% ee. The three diastereoisomeric catalysts (+)-5, (+)-6, and (-)-7 gave access to lower enantioselectivities (6 to 22% ee's), which could be rationalized by computer modeling (Fig. 4).

  DOI：

  10.1002/(sici)1522-2675(19990707)82:7<981::aid-hlca981>3.0.co;2-v

文献信息

• Isothiourea‐Catalysed Regioselective Acylative Kinetic Resolution of Axially Chiral Biaryl Diols
  作者：Shen Qu、Mark D. Greenhalgh、Andrew D. Smith

  DOI：10.1002/chem.201805631

  日期：2019.2.21

  An operationally simple isothiourea‐catalysed acylative kinetic resolution of unprotected 1,1′‐biaryl‐2,2′‐diol derivatives has been developed to allow access to axially chiral compounds in highly enantioenriched form (s values up to 190). Investigation of the reaction scope and limitations provided three key observations: i) the diol motif of the substrate was essential for good conversion and high

  已开发出一种操作简单的异硫脲催化的未保护的1,1'-联芳基-2,2'-二醇衍生物的酰基动力学拆分，可使用高度对映体富集形式的轴向手性化合物（s值高达190）。对反应范围和限制的研究提供了三个关键的观察结果：i）底物的二醇基序对于良好的转化率和高s值是必不可少的；ii）所述使用的α，α-二取代的混合酸酐（2,2-二苯乙酸新戊酸酐）对于最大程度地减少二酰化并提供高选择性至关重要。iii）二醇的3,3'-位上存在取代基阻碍了有效的酰化作用。该最终观察结果用于具有单个3-取代基的不对称联芳基二醇底物的高度区域选择性酰基动力学动力学拆分。基于确定的关键观察结果，提出了酰化过渡态模型来解释该动力学拆分的对映选择性。
• Functionalized binaphthyl salophen crown ethers as models for the enzyme urease
  作者：Arjen M. Reichwein、Willem Verboom、David N. Reinhoudt

  DOI：10.1002/recl.19931121106

  日期：——

  Functionalized binaphthyl salophen crown ethers 2 and 3 containing a Lewis-acidic uranyl cation were prepared by the Ba2+-templated cyclization of dialdehydes 15 and 22, for which two convenient synthetic routes were developed, with diamines 23 and 24. Intramolecular complexation of the amide groups in metallomacrocycles 2 and 3 was demonstrated by the isolation of two different forms of 2a, which

  通过对二醛15和22进行Ba 2+模板化的环化反应，制备了含路易斯酸酸性铀酰阳离子的功能化联萘二酚冠醚2和3，并用二胺23和24开发了两种便捷的合成途径。金属大环化合物2和3中酰胺基的分子内络合通过两种不同形式的2a的分离证明，通过1 H-NMR和IR光谱以及通过电化学测量，观察到它们相互转化。使用二胺24在环化过程中，导致单官能化的金属大环3a-d形成了两种不同的立体异构体，并且导致了双官能化的金属大环3e和3f的“偏侧性” 。分离了尿素与2c和2d的固体配合物，但在尿烷在二恶烷/水中的水解过程中，未观察到2a的催化活性。
• [EN] BINAPHTHOL ALDEHYDE DERIVATIVES AND METHOD FOR PREPARING THE SAME<br/>[FR] DÉRIVÉS DE BINAPHTOL ALDÉHYDE ET LEUR PROCÉDÉ DE PRÉPARATION
  申请人：AMINO LUX INC

  公开号：WO2010055966A1

  公开（公告）日：2010-05-20

  The present invention relates to a binaphthol aldehyde derivative represented by Chemical Formula 1 and a method of preparing the same. The binaphthol aldehyde derivative represented by Chemical Formula 1 enables various kinds of substituent groups to be very efficiently introduced into the hydrogen position of a 2' hydroxy group of 2,2'-binaphthol-3-aldehyde. The method is advantageous in that the binaphthol aldehyde derivative represented by Chemical Formula 1 can be prepared in a safe manner at low cost.

  本发明涉及一种由化学式1表示的二萘酚醛衍生物以及其制备方法。化学式1表示的二萘酚醛衍生物使得各种取代基能够非常高效地引入到2,2'-二萘酚-3-醛的2'羟基的氢位置。该方法的优点在于，可以以低成本安全地制备由化学式1表示的二萘酚醛衍生物。
• Synthesis of<i>C</i>₁-Symmetric BINOLs Employing N-Heterocyclic Carbene-Copper Complexes
  作者：Alain Grandbois、Marie-Ève Mayer、Marion Bédard、Shawn K. Collins、Typhène Michel

  DOI：10.1002/chem.200901295

  日期：2009.9.28

  Fucntionalizing BINOL: Bis‐NHCCu complexes can be used for the oxidative coupling of 2‐naphthols. Product yields are highest when using electron‐deficient 2‐naphthols. Mixed couplings between electron‐rich and electron‐poor 2‐naphthols can be conducted to give good yields of the mixed products.

  Fucntionalizing BINOL：双- NHC 铜配合物可用于氧化的2-萘酚的耦合。使用缺电子的2-萘时，产品产量最高。富电子和贫电子2-萘之间可以进行混合偶合，以得到良好的混合产物收率。
• Heterocoupling of 2-naphthols enabled by a copper–N-heterocyclic carbene complex
  作者：Michael Holtz-Mulholland、Mylène de Léséleuc、Shawn K. Collins

  DOI：10.1039/c3cc38675a

  日期：——

  The reactivity of a Cu catalyst for oxidative coupling is modulated by a small molecule additive, diethyl malonate, that slows over-oxidation of 2-naphthols. Efficient heterocoupling between electron-rich and electron-poor 2-naphthols/2-naphthylamines affords C1-symmetric BINOLs with yields ranging from 35–98%.

  氧化偶联铜催化剂的反应活性受小分子添加剂丙二酸二乙酯的调节，丙二酸二乙酯可减缓 2-萘酚的过度氧化。富电子和贫电子 2-萘酚/2-萘胺之间的高效异质偶联生成了 C1 对称的 BINOL，产率为 35%-98%。