(Rp)-trifluoromethanesulfonic acid (4-[2.2]paracyclophane) ester | 871269-22-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (Rp)-trifluoromethanesulfonic acid (4-[2.2]paracyclophane) ester
• 英文别名: (R)-trifluoromethanesulfonic acid [2.2]paracyclophan-4-yl ester；5-Tricyclo[8.2.2.24,7]hexadeca-1(13),4,6,10(14),11,15-hexaenyl trifluoromethanesulfonate
• CAS: 871269-22-6
• 化学式: C₁₇H₁₅F₃O₃S
• 分子量: 356.366
• InChiKey: KSIDZMUMAQPDNZ-UHFFFAOYSA-N

物化性质

• 沸点：
  426.3±45.0 °C(Predicted)
• 密度：
  1.355±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (Rp)-trifluoromethanesulfonic acid (4-[2.2]paracyclophane) ester 在 盐酸 、 1,1'-双(二苯基膦)二茂铁 、 tris(dibenzylideneacetone)dipalladium (0) 、 对甲苯磺酸 、 sodium t-butanolate 作用下， 以 乙醇 、 乙二醇 、 甲苯 、 苯 为溶剂， 反应 75.75h， 生成 Ethyl 12-azatetracyclo[8.5.2.24,7.011,15]nonadeca-1(15),4,6,10,13,16,18-heptaene-13-carboxylate
  参考文献：
  名称：

  Planar chiral indoles: synthesis and biological effects of the enantiomers

  摘要：

  The paracyclophanyl triflates (R)-4 and (S)-4, which were obtained from racemic precursors through enzymatic-kinetic resolution, could be employed as key intermediates for the synthesis of planar chiral [2.2](4.7)indoloparacyclophanes. Subjecting the double-layered test compounds (R)-8 and (S)-8 to in vitro ligand-binding experiments displayed stereoselective receptor recognition. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00558-4
• 作为产物：
  描述：

  4-羟基-[2.2]对环芳烷 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 (Rp)-trifluoromethanesulfonic acid (4-[2.2]paracyclophane) ester
  参考文献：
  名称：

  Synthesis of planar chiral [2.2]paracyclophane monophosphine ligands and their application in the umpolung allylation of aldehydes

  摘要：

  Chiral [2.2]paracyclophane monophosphines 8 were synthesized via resolution using chiral palladacycle 10. Chiral phosphinite 5 was also prepared from 4-hydroxy[2.2]paracyclophane. Phosphines 8 and phosphinite 5 were used as the ligand in the umpolung allylation of aldehydes 14 with cyclohexenyl acetate 15, giving homoallyl alcohols 16 in high diastereoselectivity and in moderate to good enantioselectivity. Palladacycle 10 was recovered by treating the palladacycle-phosphine complexes with sodium prolinate, followed by treatment with HCl in high yield. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2007.01.020

文献信息

• Diastereoselective Hartwig–Buchwald Reaction of Chiral Amines withrac-[2.2]Paracyclophane Derivatives
  作者：Michael Kreis、Christian J. Friedmann、Stefan Bräse

  DOI：10.1002/chem.200500386

  日期：2005.12.9

  rac-4-bromo-[2.2]paracyclophane and rac-trifluoromethanesulfonic acid (4-[2.2]paracyclophane) ester was performed with high diastereoselectivities. Kinetic racemic resolution of the starting materials was achieved, providing a rapid access to enantiomerically enriched 4-bromo-[2.2]paracyclophane and the corresponding enantiomerically pure [2.2]paracyclophane amines. Additionally, the first reaction of a secondary

  Hartwig-Buchwald将多种手性胺加至rac-4-溴-[2.2]对环环烷和rac-三氟甲磺酸（4- [2.2]对环环烷）酯中，具有很高的非对映选择性。达到了原料的动力学外消旋拆分，可以快速获得对映体富集的4-溴-[2.2]对环环糊精和相应的对映体纯的[2.2]对环环糊精胺。另外，实现了仲胺与[2.2]对环环烷卤化物的第一反应。
• A General and Efficient Method for the Synthesis of Silyl-Protected Arenethiols from Aryl Halides or Triflates
  作者：Michael Kreis、Stefan Bräse

  DOI：10.1002/adsc.200404299

  日期：2005.2

  An improved palladium-catalyzed synthesis of silyl-protected arenethiols has been developed. This method is particularly useful because of its experimental simplicity, high generality and high level of functional group toleration. The first synthesis of enantiomerically pure [2.2]paracyclophane-4-thiol was realized employing this method.

  已经开发了改进的钯催化的甲硅烷基保护的芳硫醇的合成。该方法由于其实验简单，高度通用性和高水平的官能团耐受性而特别有用。采用这种方法可以实现对映体纯的[2.2]对环烷-4-硫醇的首次合成。
• Planar-chiral imidazole-based phosphine ligands derived from [2.2]paracyclophane
  作者：Richard J. Seacome、Martyn P. Coles、Jean E. Glover、Peter B. Hitchcock、Gareth J. Rowlands

  DOI：10.1039/b923716j

  日期：——

  planar chiral heteroaryl monophosphines have been synthesised and studied. The phosphines are readily prepared from 4-imidazole[2.2]paracyclophane by selective deprotonation and reaction with the appropriate dialkylchlorophosphines. The planar chiral imidazole was constructed in four steps from readily available [2.2]paracyclophane. The 2-phosphino-N-[2.2]paracyclophanes were active in the Suzuki–Miyaura

  已经合成和研究了两种平面手性杂芳基单膦。膦很容易从4-咪唑[2.2]对环环烷通过选择性去质子化并与适当的二烷基氯膦反应。平面手性咪唑可从四步中获得[2.2]对环。2-膦基-N- [2.2]对环环烷在芳基溴化物和氯化物的Suzuki-Miyaura偶联中具有活性。协调研究表明，固态的P，N螯合。这些研究为非对称耦合奠定了基础。
• Analogs of the dopamine D4 receptor ligand FAUC 113 with planar- and central-chirality
  作者：Stefan Löber、Birgit Ortner、Laura Bettinetti、Harald Hübner、Peter Gmeiner

  DOI：10.1016/s0957-4166(02)00639-0

  日期：2002.10

  employing yeast enzymes, natural amino acids and the Jacobsen's catalyst as sources of chirality, we have synthesized pyrazolo[1,5-a]pyridine derivatives with central- and planar-chirality as analogs of the dopamine D4 receptor ligand FAUC 113. In vitro binding experiments displayed enhanced D2 and D3 affinity for both enantiomers of the [2.2]paracyclophane 3. The C-methylpiperazine (R)-4a revealed excellent D4 selectivity. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Synthesis of planar chiral [2.2]paracyclophane monophosphine ligands and their application in the umpolung allylation of aldehydes
  作者：Tang-Zhi Zhang、Li-Xin Dai、Xue-Long Hou

  DOI：10.1016/j.tetasy.2007.01.020

  日期：2007.2

  Chiral [2.2]paracyclophane monophosphines 8 were synthesized via resolution using chiral palladacycle 10. Chiral phosphinite 5 was also prepared from 4-hydroxy[2.2]paracyclophane. Phosphines 8 and phosphinite 5 were used as the ligand in the umpolung allylation of aldehydes 14 with cyclohexenyl acetate 15, giving homoallyl alcohols 16 in high diastereoselectivity and in moderate to good enantioselectivity. Palladacycle 10 was recovered by treating the palladacycle-phosphine complexes with sodium prolinate, followed by treatment with HCl in high yield. (c) 2007 Elsevier Ltd. All rights reserved.