rac-10,10'-dihydroxy-9,9'-biphenanthryl | 110071-78-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: rac-10,10'-dihydroxy-9,9'-biphenanthryl
• 英文别名: [9,9'-biphenanthrene]-10,10'-diol；10-(10-hydroxyphenanthren-9-yl)phenanthren-9-ol
• CAS: 110071-78-8
• 化学式: C₂₈H₁₈O₂
• 分子量: 386.45
• InChiKey: AIRSOVDICMIOKM-UHFFFAOYSA-N

物化性质

• 熔点：
  154-155 °C
• 沸点：
  594.0±45.0 °C(Predicted)
• 密度：
  1.341±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  30
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  rac-10,10'-dihydroxy-9,9'-biphenanthryl 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 107.0h， 生成 17-[3-(16,18-Dioxa-17-phosphaheptacyclo[17.12.0.02,15.03,8.09,14.020,25.026,31]hentriaconta-1(19),2(15),3,5,7,9,11,13,20,22,24,26,28,30-tetradecaen-17-yloxy)-2-iodophenoxy]-16,18-dioxa-17-phosphaheptacyclo[17.12.0.02,15.03,8.09,14.020,25.026,31]hentriaconta-1(19),2(15),3,5,7,9,11,13,20,22,24,26,28,30-tetradecaene
  参考文献：
  名称：

  Synthesis and Catalytic Application of Chiral 1,1‘-Bi-2-naphthol- and Biphenanthrol-Based Pincer Complexes:  Selective Allylation of Sulfonimines with Allyl Stannane and Allyl Trifluoroborate

  摘要：

  New easily accessible 1,1'-bi-2-naphthol- (BINOL-) and biphenanthrol-based chiral pincer complex catalysts were prepared for selective (up to 85% enantiomeric excess) allylation of sulfonimines. The chiral pincer complexes were prepared by a flexible modular approach allowing an efficient tuning of the selectivity of the catalysts. By employment of the different enantiomeric forms of the catalysts, both enantiomers of the homoallylic amines could be selectively obtained. Both allyl stannanes and allyl trifluoroborates can be employed as allyl sources in the reactions. The biphenanthrol-based complexes gave higher selectivity than the substituted BINOL-based analogues, probably because of the well-shaped chiral pocket generated by employment of the biphenanthrol complexes. The enantioselective allylation of sulfonimines presented in this study has important implications for the mechanism given for the pincer complex-catalyzed allylation reactions, confirming that this process takes place without involvement of palladium(0) species.

  DOI：

  10.1021/jo070288b
• 作为产物：
  描述：

  在 盐酸 、 红铝 作用下， 以 乙醚 、 乙醇 、 甲苯 为溶剂， 反应 4.5h， 生成 rac-10,10'-dihydroxy-9,9'-biphenanthryl
  参考文献：
  名称：

  Two methods for the resolution of 10,10′-dihydroxy-9,9′-biphenanthryl

  摘要：

  Two methods for the resolution of 10,10'-dihydroxy-9,9'-biphenanthryl were developed. The first involved salt formation with (-)-strychnine via its cyclic diester with phosphoric acid. The second method involved the formation of diastereomers (R)- and (S)-9,9'-biphenanthryl-10,10'-diyl N-((-)-alpha-methylbenzyl)phosphoroamidates. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(97)00618-6
• 作为试剂：
  描述：

  4-氯-3-羟基丁酸甲酯 、 (+)-10,10'-dihydroxy-9,9'-biphenanthryl 在 rac-10,10'-dihydroxy-9,9'-biphenanthryl 作用下， 以58%的产率得到[9,9']Biphenanthrenyl-10,10'-diol; compound with 4-chloro-3-hydroxy-butyric acid methyl ester
  参考文献：
  名称：

  一种新的手性主体化合物10,10'-dihyrroxy-9,9'-biphenanthryl。丙酸衍生物，丁酸衍生物和4-羟基环戊-2-烯-1-酮衍生物的旋光拆分

  摘要：

  旋光的10,10'-二羟基-9,9'-联菲被设计为一种新的手性主体化合物，用于光学拆分客体化合物，并被发现对于标题客体化合物的拆分非常有效。

  DOI：

  10.1016/s0040-4039(00)82049-3

文献信息

• METHOD FOR MANUFACTURING OPTICALLY ACTIVE MENTHOL
  申请人：Tsuda Toshiro

  公开号：US20130253228A1

  公开（公告）日：2013-09-26

  An object of the present invention is to provide a method for manufacturing an optically active menthol having fewer steps, which generates less environmentally polluting waste because a catalytic reaction is involved in all of the steps, and is capable of saving a production cost. The present invention relates to a method for manufacturing an optically active menthol, including the following steps: A-1) asymmetrically hydrogenating at least one of geranial and neral to thereby obtain an optically active citronellal, B-1) conducting a ring-closure reaction of the optically active citronellal in the presence of an acid catalyst to thereby obtain an optically active isopulegol, and C-1) hydrogenating the optically active isopulegol to thereby obtain an optically active menthol.

  本发明的目的是提供一种制造具有较少步骤的光学活性薄荷醇的方法，因为所有步骤都涉及催化反应，所以产生的环境污染废物较少，并且能够节省生产成本。本发明涉及一种制造光学活性薄荷醇的方法，包括以下步骤：A-1）不对称地氢化至少一种香叶醛和柠檬醛以获得光学活性柠檬醛，B-1）在酸催化剂存在下对光学活性柠檬醛进行环闭合反应，从而获得光学活性异薄荷醇，以及C-1）对光学活性异薄荷醇进行氢化以获得光学活性薄荷醇。
• Chirality Transfer from the Oxidative Dearomatization of Axially Chiral Binols with Oxone under Mild Conditions
  作者：Antonio Urbano、Sara Vallejo、María J. Cabrera-Afonso、Elena Yonte

  DOI：10.1021/acs.orglett.0c02194

  日期：2020.8.7

  Easily accessible axially chiral substituted binols (95 to >99% ee) undergo an oxidative dearomatization process with the system Oxone/NaHCO3/acetone, under mild conditions, to afford pentacyclic hemiacetalic cis-diols (94 to >99% ee), bearing two new stereogenic centers, through an efficient axial-to-central chirality transfer.

  容易获得的轴向手性取代的二元醇（95至> 99％ee）在温和的条件下用Oxone / NaHCO 3 /丙酮体系进行氧化脱芳香化过程，得到五环半缩醛顺式二醇（94至> 99％ee），通过有效的轴向向中心手性传递，建立了两个新的立体生成中心。
• Structural, Mechanistic, Spectroscopic, and Preparative Studies on the <i>Lewis</i> Base Catalyzed, Enantioselective Sulfenofunctionalization of Alkenes
  作者：Eduard Hartmann、Scott E. Denmark

  DOI：10.1002/hlca.201700158

  日期：2017.9

  with the spectroscopic identification of putative thiiranium ion intermediates generated in the enantiodetermining step. The structural insights gleaned from these studies informed the design of new catalyst architectures to improve enantioselectivity. In addition, structural modification of the sulfenylating agents had a significant and salutary effect on the enantioselectivity of sulfenofunctionalization

  刘易斯条件下烯烃对映选择性磺基官能化机理研究的全部细节描述了碱催化。催化活性的亚磺酰化剂的溶液光谱鉴定与对映体确定步骤中产生的推定的硫鎓离子中间体的光谱鉴定已经完成。从这些研究中获得的结构见解为改进对映选择性的新型催化剂结构的设计提供了参考。另外，亚磺酰化剂的结构改性对磺基官能化的对映选择性具有显着的有益作用，这被证明对于反式二取代烯烃是普遍的。尽管电子调制对速率和选择性几乎没有影响，但芳基亚硫基邻苯二甲酰亚胺的空间体积非常有益。
• Synthesis of structurally diversified BINOLs and NOBINs via palladium-catalyzed C-H arylation with diazoquinones
  作者：Ji-Wei Zhang、Fei Jiang、Ye-Hui Chen、Shao-Hua Xiang、Bin Tan

  DOI：10.1007/s11426-021-1003-9

  日期：2021.9

  efficiently constructed with sole 1-DNQs as arylation reagents under one set of reaction conditions. The judicious selection of palladium catalytic system plays a pivotal role in the excellent selectivities. This transformation accommodated fairly broad substrate generality for both 2-naphthol and N-Boc-2-naphthylamine and afforded the structurally diversified BINOLs and NOBIN derivatives in high efficiency

  在一组反应条件下，使用唯一的 1-DNQ 作为芳基化试剂有效地构建了特权联芳基框架 BINOL 和 NOBIN。钯催化体系的明智选择对优异的选择性起着关键作用。这种转变为 2-萘酚和N提供了相当广泛的底物通用性-Boc-2-萘胺并高效地提供了结构多样化的BINOLs和NOBIN衍生物。值得注意的是，在常规钯催化反应中无法存活的溴取代基与这组条件非常兼容，为进一步丰富 BINOL 和 NOBIN 库提供了有效的手段。对该反应的不对称变体也进行了初步尝试，用于 BINOLs 合成的比例高达 80:20。
• 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。

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