(S)-1H-1-(2-bromophenyl)perfluorooctan-1-ol | 881693-13-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-1H-1-(2-bromophenyl)perfluorooctan-1-ol
• 英文别名: (S)-1-bromo-2-(1-hydroxy-1H-perfluorooctyl)benzene；(1S)-1-(2-bromophenyl)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctan-1-ol
• CAS: 881693-13-6
• 化学式: C₁₄H₆BrF₁₅O
• 分子量: 555.081
• InChiKey: KCYKCPJLNOPGRP-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  (S)-1H-1-(2-bromophenyl)perfluorooctan-1-ol 在 bis(1,5-cyclooctadiene)nickel (0) sodium hydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 27.0h， 生成 (Sa)-2,2'-bis[(S)-1-hydroxy-1H-perfluorooctyl]biphenyl
  参考文献：
  名称：

  New axially dissymmetric ligand recoverable with fluorous solvent

  摘要：

  Axially dissymmetric ligands with perfluoroalkyl groups, (Ra)-2,2'-bis[(R)-1-hydroxy-1H-perfluorooctyl]biphenyl [(Ra)-(R)(2)-1c] and its enantiomer, have been synthesized successfully by the coupling reaction of the corresponding aryl bromide using Ni(COD)(2). These ligands showed much higher asymmetric induction in the reaction of various aldehydes with diethylzinc than the trifluoromethyl (1a) or pentafluoroethyl (1b) analogues. Furthermore, 1c was recovered quantitatively by extraction with a fluorous solvent from the reaction mixture due to its high fluorine content. The recovered ligand 1c was pure enough to be reused without purification. The efficiency of 1c as the chiral ligand was not decreased at all even after seven times recycling (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.11.063
• 作为产物：
  描述：

  1-(2-bromophenyl)perfluorooctan-1-one 在 (S)-2-甲基-CBS-恶唑硼烷 、 儿萘酚硼烷 作用下， 以 四氢呋喃 为溶剂， 以97%的产率得到(S)-1H-1-(2-bromophenyl)perfluorooctan-1-ol
  参考文献：
  名称：

  New axially dissymmetric ligand recoverable with fluorous solvent

  摘要：

  Axially dissymmetric ligands with perfluoroalkyl groups, (Ra)-2,2'-bis[(R)-1-hydroxy-1H-perfluorooctyl]biphenyl [(Ra)-(R)(2)-1c] and its enantiomer, have been synthesized successfully by the coupling reaction of the corresponding aryl bromide using Ni(COD)(2). These ligands showed much higher asymmetric induction in the reaction of various aldehydes with diethylzinc than the trifluoromethyl (1a) or pentafluoroethyl (1b) analogues. Furthermore, 1c was recovered quantitatively by extraction with a fluorous solvent from the reaction mixture due to its high fluorine content. The recovered ligand 1c was pure enough to be reused without purification. The efficiency of 1c as the chiral ligand was not decreased at all even after seven times recycling (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.11.063

文献信息

• Asymmetric reduction of perfluoroalkyl ketones with chiral lithium alkoxides
  作者：Yasser Samir Sokeirik、Kazuyuki Sato、Masaaki Omote、Akira Ando、Itsumaro Kumadaki

  DOI：10.1016/j.tetlet.2006.02.078

  日期：2006.4

  Reduction of perfluoroalkyl ketones with chiral lithium alkoxides gave chiral α-perfluoroalkyl alcohols in high enantiomeric excesses. Interestingly, reaction of 2,2,2-trifluoroacetophenone (1) with lithium (S)-1-phenylethoxide (2) gave (S)-2,2,2-trifluoro-1-phenylethanol (3), while the same reaction of perfluorooctan-1-one (7) with 2 gave (R)-1H-1-phenylperfluorooctanol (8). Based on the speculation

  用手性烷醇锂还原全氟烷基酮得到高对映体过量的手性α-全氟烷基醇。有趣的是，2,2,2-三氟苯乙酮（1）与（S）-1-苯基乙氧基锂（2）反应生成（S）-2,2,2,2-三氟-1-苯乙醇（3），而相同的反应将全氟辛烷-1-酮（7）与2进行反应，得到（R）-1 H -1-苯基全氟辛醇（8）。根据机理推测，该反应的空间效应顺序为C 7 F 15  >取代苯基> CF 3。