2,2'-bis-allyloxy-1,1'-binaphthyl | 59031-18-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2,2'-bis-allyloxy-1,1'-binaphthyl
• 英文别名: 2-prop-2-enoxy-1-(2-prop-2-enoxynaphthalen-1-yl)naphthalene
• CAS: 59031-18-4
• 化学式: C₂₆H₂₂O₂
• 分子量: 366.459
• InChiKey: PDJRJPSZXDUOPD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2'-bis-allyloxy-1,1'-binaphthyl 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 作用下， 以 二氯甲烷 为溶剂， 反应 0.1h， 以93%的产率得到Z-4,7-dihydrodinaphtho[2,1-b:1',2'-d][1,6]dioxecine
  参考文献：
  名称：

  Synthesis of Z-di/tetra/hexa/ydrodinaphtho[2,1-b:1′,2′-d][1,6]dioxacycloalkenes via microwave-accelerated ring closing metathesis and their antimicrobial activity

  摘要：

  Z-Di/tetra/hexa/hydrodinaphtho[2,1-b:1',2'-d][1,6]dioxacycloalkenes have been synthesized under microwave-accelerated ring closing metathesis (RCM) of 2,2'-bis(alkenyloxy)-1,1'-binaphthalenes. Microwave irradiation improved the efficiency of ring closing metathesis and dramatically reduced reaction time. Structures of newly synthesized compounds have been elucidated by means of elemental analysis, IR, H-1 and C-13 NMR and mass spectral data. All compounds were tested for their antibacterial activity against Grampositive bacteria Staphylococcus aureus, Bacillus subtilis and Gram-negative bacteria Pseudomonas aeruginosa, Escherichia coli and antifungal activity against fungal strains Aspergillus niger, Penicillium italicum and Fusarium oxysporum.

  DOI：

  10.1134/s1070363215050254
• 作为产物：
  描述：

  (S)-(-)-2,2'-bis(2-methylallyloxy)-1,1'-binaphthalenyl 在 potassium carbonate 、 均三甲苯 作用下， 以 丙酮 为溶剂， 生成 2,2'-bis-allyloxy-1,1'-binaphthyl
  参考文献：
  名称：

  Binaphthyls系列中的分子内环加成†

  摘要：

  联萘化合物的分子内缩合

  DOI：

  10.1002/hlca.19750580711

文献信息

• Synthesis and binding properties of chiral macrocyclic barbiturate receptors: application to nitrile oxide cyclizations
  作者：Brian S. Rasmussen、Unai Elezcano、Troels Skrydstrup

  DOI：10.1039/b110865b

  日期：2002.7.11

  A series of chiral macrocyclic receptors containing a barbiturate binding domain based on two 2,6-diaminopyridine groups has been synthesized with the purpose of exploiting these for asymmetric 1,3-dipolar cycloadditions. Each macrocyclic host was built possessing an (R)-BINOL or a modified deoxycholate moiety as the chiral unit connected to the barbiturate binding domain with varying lengths of spacer. All the hosts with the exception of one were found to effectively bind a barbiturate–cinnamic acid conjugate with association constants in the order of 104 M−1 in CDCl3. The 1,3-dipolar cycloaddition between several arylnitrile oxides and the cinnamate conjugates were examined in the presence of stoichiometric amounts of a chiral receptor affording two regioisomeric isoxazolines. Enantiomeric excesses of up to 30% were obtained in one case for the major regioisomer. In most cases, the enantiomeric excesses could be measured directly from the crude 1H-NMR spectra owing to the diastereomeric interaction between the isoxazoline cycloadduct and the chiral receptor. The relatively low enantiofacial selectivities at the CC double bond of the cinnamate were attributed to the non-planar orientation of the barbiturate–cinnamate conjugate with respect to the receptor, as previously noted for the binding of barbital to an achiral macrocyclic host (S.-K., Chang, E. Fan, D. Van Engen and A. D. Hamilton, J. Am. Chem. Soc., 1991, 113, 7640), directing the cinnamate unit away from the chiral unit.

  一系列基于两个2,6-二氨基吡啶基团的巴比妥酸盐结合域的手性大环受体已被合成，旨在利用它们进行不对称的1,3-偶极环加成反应。每个大环主体构建时含有一个(R)-BINOL或修饰的脱氧胆酸部分作为手性单元，通过不同长度的间隔基与巴比妥酸盐结合域相连。除一种外，所有受体均能有效结合巴比妥酸盐-肉桂酸共轭物，其在CDCl3中的结合常数为10^4 M^-1数量级。在手性受体的定量存在下，考察了几种芳基腈氧化物与肉桂酸共轭物之间的1,3-偶极环加成反应，生成两种区域异构的异恶唑啉。在某例中，主要区域异构体的对映体过量达到30%。在多数情况下，由于异恶唑啉环加合物与手性受体之间的非对映异构相互作用，对映体过量可以直接从粗1H-NMR谱图中测得。肉桂酸在CC双键处的相对较低的对映选择性归因于巴比妥酸盐-肉桂酸共轭物相对于受体的非平面取向，这一点与以前报道的巴比妥酸盐与非手性大环受体的结合情况相似（Chang等，1991），导致肉桂酸部分远离手性单元。
• Tandem RCM–Claisen Rearrangement–[2+2] Cycloaddition of O,O'-(But-2-en-1,4-diyl)-bridged Binaphthols
  作者：Michael Abraham、Wolfgang Reischl、Karl Kirchner、Alexander Roller、Luis Veiros、Michael Widhalm

  DOI：10.3390/molecules171214531

  日期：——

  Attempted RCM of 2,2'-bis(allyloxy)-1,1'-binaphthyl resulted in a Claisen-type rearrangement of a postulated labile dioxacyclodecine proceeding at room temperature and followed by [2+2] cycloaddition. Structures of products were confirmed by X-ray crystallography. A mechanistic rationalisation based on relative stabilities of proposed intermediates and transition states is provided.

  对2,2'-双(烯丙氧基)-1,1'-联萘的尝试RCM反应导致假设的不稳定二氧周期癸烯在室温下发生Claisen型重排，随后进行[2+2]环加成。产物的结构通过X射线晶体学得到了确认。本文提供了基于提出的中间体和过渡态相对稳定性的机理解释。
• Embedding an Allylmetal Dimer in a Chiral Cavity:  The Unprecedented Stereoselectivity of a Twofold Wittig [1,2]-Rearrangement
  作者：Manfred Schlosser、Frédéric Bailly

  DOI：10.1021/ja066462f

  日期：2006.12.1

  alpha'-dimetalation, both 2,2'-diallyloxy-1,1'-binaphthyl and 2,2'-di-2-methylallyloxy-1,1'-binaphthyl undergo the Wittig rearrangement with perfect diastereoselectivity. When racemic 1,1'-binaphthyl-2,2'-diol ("BINOL") is used as the starting material, it gives rise to a 1:1 mixture of antipodal stereoisomers, whereas enantiomerically pure (M)-2,2'-diallyloxy-1,1'-binaphthyl affords (M)-(S,S)-1,1-(1,1'-binaphthyl-2

  在 alpha,alpha'-dimetalation 之后，2,2'-diallyloxy-1,1'-binaphthyl 和 2,2'-di-2-methylallyloxy-1,1'-binaphthyl 都经过 Wittig 重排，具有完美的非对映选择性。当外消旋 1,1'-联萘-2,2'-二醇（“BINOL”）用作起始材料时，它会产生 1:1 的对映体立体异构体混合物，而对映体纯 (M)-2,2 '-diallyloxy-1,1'-binaphthyl 提供 (M)-(S,S)-1,1-(1,1'-binaphthyl-2,2'-diyl)bis(2-propen-1-ol)作为唯一的产品。由外消旋 2,2'-二烯丙氧基-1,1'-联萘重排产生的 (M)-(S,S)/(P)-(R,R) 混合物可以有效地进行动力学外消旋体拆分应用 Sharpless-Katsuki 不对称环氧化。2-烯丙氧基-2'-丙氧基-1
• Synthesis of Enantiomerically Pure Thiocrown Ethers Derived from 1,1‘-Binaphthalene-2,2‘-diol
  作者：H. Thijs Stock、Richard M. Kellogg

  DOI：10.1021/jo952107o

  日期：1996.1.1

  Synthetic methodology is given for the preparation of two different types of thiocrown ethers from optically pure 1,1'-binaphthalene-2,2'-diol (10). The conceptually simplest approach starts from optically pure 10 itself, which is alkylated (4 equiv of K(2)CO(3) in DMF at 110 degrees C) with 2-chloroethanol followed by mesylation to provide 2,2'-bis(2-(mesyloxy)ethoxy)-1,1'-binaphthyl (14). When allowed

  给出了从光学纯的1,1'-联萘-2,2'-二醇（10）制备两种不同类型的硫代冠醚的合成方法。从概念上讲，最简单的方法是从光学纯的10本身开始，将其与2-氯乙醇进行烷基化（在DMF中于110摄氏度时在DMF中为4当量的K（2）CO（3）），然后进行甲磺酰化，以提供2,2'-bis（2 -（甲甲氧基）乙氧基）-1,1'-联萘基（14）。当使其与乙烷-1,2-二硫醇，丙烷-1,3-二硫醇，1,4,7-三噻庚烷，1,4,8,11-四硫十一烷，2,2-二甲基丙烷-1,3-二硫醇反应时，2-（巯基甲基）-1-丙烯-3-硫醇和1,2-苯二硫醇在Cs（2）CO（3）在60°C的DMF中存在时，相应的硫冠醚22-25、28、30 ，以30-54％的产率形成32。进行测试反应以证实在这些条件下在烷基化过程中不发生外消旋化。在相似的条件下，将光学纯的10与四氢吡喃基（THP）保护的3-氯丙醇的反应进行得较慢，但反应较干净。除去THP保护基，得到2
• Ruthenium(IV)‐Catalyzed Isomerization of the CC Bond of<i>O</i>‐Allylic Substrates: A Theoretical and Experimental Study
  作者：Adrián Varela‐Álvarez、José A. Sordo、Estefanía Piedra、Noel Nebra、Victorio Cadierno、José Gimeno

  DOI：10.1002/chem.201101131

  日期：2011.9.12

  carried out in aqueous medium. The new mechanistic proposal helped to develop a new experimental procedure for isomerization of allyl ethers to 1‐propenyl ethers under neutral aqueous conditions. This process is an unique example of efficient and selective catalytic isomerization of allyl ethers in aqueous medium.

  一般机制来合理化茹IV催化的所述CC键的异构化在ö建议使用烯丙基底物。在MPWB1K / 6-311 + G（d，p）+ SDD的理论水平上进行了支持该机制的计算。可以根据新机理解释在不同溶剂（水和THF）和不同pH条件（中性和碱性）下的所有实验观察结果。从预催化剂到催化剂的转化的理论分析导致了在不同介质中活性物种的结构鉴定。实验观察到的诱导期与为该过程计算的能垒的大小有关。如实验观察到的，催化循环的理论能量分布需要施加相对较高的温度。当在水性介质中进行反应时，水分子参与反应坐标是机械上必不可少的。新的机理建议有助于开发一种新的实验程序，用于在中性水溶液条件下将烯丙基醚异构化为1-丙烯基醚。该方法是烯丙基醚在水性介质中有效和选择性催化异构化的独特实例。