(R)-(-)-3,3'-bis(trifluoromethanesulfonyloxy)-4,4'-biphenanthryl

• 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: (R)-(-)-3,3'-bis(trifluoromethanesulfonyloxy)-4,4'-biphenanthryl
• 英文别名: (R)-[4,4'-biphenanthrene]-3,3'-diyl-bis-trifluoromethanesulfonate；(R)-[4,4’-biphenanthrene]-3,3’-diyl bis(trifluoromethanesulfonate)；4,4'-Biphenanthrene-3,3'-diylbis(trifluoromethanesulfonate)；[4-[3-(trifluoromethylsulfonyloxy)phenanthren-4-yl]phenanthren-3-yl] trifluoromethanesulfonate
• 化学式: C₃₀H₁₆F₆O₆S₂
• 分子量: 650.576
• InChiKey: IDLPZJQPTYCKTJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.1
• 重原子数：
  44
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (R)-(-)-3,3'-bis(trifluoromethanesulfonyloxy)-4,4'-biphenanthryl 在 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) N-溴代丁二酰亚胺(NBS) 、 (PhCO₂)2O 作用下， 以 四氢呋喃 、 四氯化碳 为溶剂， 反应 1.25h， 生成 3-(Bromomethyl)-4-[3-(bromomethyl)phenanthren-4-yl]phenanthrene
  参考文献：
  名称：

  Synthesis of carbohelicenes and derivatives by “carbenoid couplings”

  摘要：

  Short synthetic sequences to carbohelicenes have been achieved under thermal conditions, without using photochemistry and high dilution. Couplings of aromatic bis(bromomethyl) moieties, in the presence of an excess of LiHMDS, are key reactions in the final ring closures to carbohelicenes. These optimized, quick and efficient reactions occur at 0 degrees C within 10 min, and often provide [5]-helicene, [5] helicene derivatives and [7]-helicene in similar to 75% yield. Preliminary data questioned the formation of carbenoid anions and carbenes in the so called "carbenoid couplings". (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02670-7
• 作为产物：
  描述：

  3-菲醇 在 吡啶 、 di-μ-hydroxo-bis[(N,N,N′,N′-tetramethylethylenediamine)copper(II)] chloride 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 (R)-(-)-3,3'-bis(trifluoromethanesulfonyloxy)-4,4'-biphenanthryl
  参考文献：
  名称：

  嵌入[7]象丙二烯骨架的三苯甲基阳离子：制备和作为路易斯酸催化剂的应用

  摘要：

  报道了螺旋手性碳正离子的合成。新的基序本质上是嵌入[7]螺旋状骨架中的三苯甲基阳离子。其制备的关键步骤是通过空前的钯催化4,4'-联菲基-3,3'-二基前体的羰基环化反应一步建立π-扩展芴酮体系。发现新的碳路易斯酸的外消旋形式催化通常由三苯甲基阳离子促进的一组代表性反应。

  DOI：

  10.1055/a-1404-4966

文献信息

• A New Optically Active Monodentate Phosphine Ligand, (<i>R</i>)-(+)-3-Diphenylphosphino-3′-methoxy-4,4′-biphenanthryl (MOP-phen): Preparation and Use for Palladium-Catalyzed Asymmetric Reduction of Allylic Esters with Formic Acid
  作者：Tamio Hayashi、Hiroshi Iwamura、Yasuhiro Uozumi、Yonetatsu Matsumoto、Fumiyuki Ozawa

  DOI：10.1055/s-1994-25517

  日期：——

  (R)-(+)-3-Diphenylphosphino-3′-methoxy-4,4′-biphenanthryl (MOP-phen, 8) was prepared starting with (-)-3,3′-dihydroxy-4,4′-biphenanthryl. The absolute configuration of (+)-8 was determined to be R by X-ray crystal structure analysis of its π-allylpalladium complex. The monodentate optically active phosphine 8 was found to be a more enantioselective ligand than (R)-(+)-2-diphenylphosphino-2′-methoxy-1,1′-binaphthyl (MOP, 1a) for palladium-catalyzed asymmetric reduction of allylic esters with formic acid giving optically active olefins of up to 85% ee.

  (R)-(+)-3-二苯基膦-3′-甲氧基-4,4′-双菲基（MOP-phen，8）的制备始于(-)-3,3′-二羟基-4,4′-双菲基。通过其π-烯丙基钯络合物的X射线晶体结构分析，确定了(+)-8的绝对构型为R。单齿光学活性膦配体8被发现比(R)-(+)-2-二苯基膦-2′-甲氧基-1,1′-联萘基（MOP，1a）在钯催化的烯丙基酯不对称还原反应中具有更高的对映选择性，使用甲酸作为还原剂可得到高达85% ee的光学活性烯烃。
• One-Pot Preparation of (<i>NH</i>)-Phenanthridinones and Amide-Functionalized [7]Helicene-like Molecules from Biaryl Dicarboxylic Acids
  作者：Takuya Murai、Yongning Xing、Mayu Kurokawa、Toshifumi Kuribayashi、Masanori Nikaido、Elghareeb E. Elboray、Shohei Hamada、Yusuke Kobayashi、Takahiro Sasamori、Takeo Kawabata、Takumi Furuta

  DOI：10.1021/acs.joc.1c02769

  日期：2022.5.6

  A one-pot transformation of biaryl dicarboxylic acids to (NH)-phenanthridinone derivatives based on a Curtius rearrangement and subsequent basic hydrolysis was developed. This method is also applicable for the preparation of optically active amide-functionalized [7]helicene-like molecules. Furthermore, aza[5]helicene derivatives with a phosphate moiety were isolated as a product of the Curtius rearrangement

  开发了基于 Curtius 重排和随后的碱性水解的联芳基二羧酸向 ( NH )-菲啶酮衍生物的一锅法转化。该方法也适用于光学活性酰胺官能化[7]类螺烯分子的制备。此外，在带有硫属元素原子的底物的情况下，具有磷酸盐部分的氮杂[5]螺烯衍生物被分离为 Curtius 重排步骤的产物。通过 X 射线衍射分析揭示了这些产品的立体结构，表明硫属元素键合和磷元素键合相互作用可能有助于它们的稳定性。进一步研究了类螺烯分子的构型稳定性及其手性。
• Benzylic-type couplings provide an important asymmetric entry to functionalized, non-racemic helicenes
  作者：Vincent Terrasson、Myriam Roy、Stéphane Moutard、Marie-Pier Lafontaine、Gérard Pèpe、Guy Félix、Marc Gingras

  DOI：10.1039/c4ra04398g

  日期：——

  Benzylic-type couplings are key reactions to make non-racemic helicenes.

  苯基型偶联反应是制备非消旋螺旋烯的关键反应。
• Enantioselective Synthesis of [7]Helicene: Dramatic Effects of Olefin Additives and Aromatic Solvents in Asymmetric Olefin Metathesis
  作者：Alain Grandbois、Shawn K. Collins

  DOI：10.1002/chem.200801033

  日期：2008.10.20

  The asymmetric synthesis of [7]helicene was accomplished in good ee (80%) by kinetic resolution by means of asymmetric olefin metathesis. Three key factors contributed to the success of the kinetic resolution: the use of new Ru-based olefin metathesis catalysts bearing C1-symmetric N-heterocyclic carbene ligands, simple olefins as additives to control the nature of the propagating alkylidene and hexafluorobenzene

  [7]螺旋烯的不对称合成通过不对称烯烃复分解的动力学拆分以良好的ee（80％）完成。动力学拆分成功的三个关键因素：使用带有C1对称N-杂环卡宾配体的新型Ru基烯烃复分解催化剂，简单的烯烃作为添加剂来控制传播的亚烷基和六氟苯作为溶剂的性质。
• λ5-Phospha[7]helicenes: Synthesis, Properties, and Columnar Aggregation with One-Way Chirality
  作者：Koji Nakano、Hiromi Oyama、Yoshio Nishimura、Satoshi Nakasako、Kyoko Nozaki

  DOI：10.1002/anie.201106157

  日期：2012.1.16

  One‐way street: A new family of λ5‐phospha[7]helicenes which form one‐dimensional columnar stacks in the solid state were synthesized (see scheme). Neighboring stacks have opposite dipole directions and, in the case of the racemic phosphole sulfide based helicene, columns with a given dipole direction consist of one enantiomer, whereas columns with the opposite dipole direction consist of the other

  单向街道：λ的新家族5-磷[7]，其形成在固态的一维柱状叠层合成helicenes（参见方案）。相邻的叠层具有相反的偶极方向，在外消旋的基于磷硫醚的螺旋烯的情况下，具有给定的偶极方向的柱由一种对映体组成，而具有相反的偶极方向的柱则由另一种对映体组成。