(4S,14S)-(+)-4,14-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-trien-19-yl trifluoromethanesulfonate | 1380421-67-9

• 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: (4S,14S)-(+)-4,14-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-trien-19-yl trifluoromethanesulfonate
• 英文别名: [(4S,14S)-4,14-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]henicosa-1(20),17(21),18-trien-19-yl] trifluoromethanesulfonate
• CAS: 1380421-67-9
• 化学式: C₁₈H₂₆F₃NO₈S
• 分子量: 473.468
• InChiKey: NTVZGJVYSWHXOT-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  31
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  111
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (4S,14S)-(+)-4,14-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-trien-19-yl trifluoromethanesulfonate 在 盐酸 、 potassium phosphate 、 四(三苯基膦)钯 、 sodium iodide 、 potassium bromide 作用下， 以 1,4-二氧六环 、 水 、 乙腈 为溶剂， 反应 10.0h， 生成 methyl 4-[(4S,14S)-()-4,14-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-trien-19-yl]-benzoate
  参考文献：
  名称：

  Preparation of pyridino-crown ether-based new chiral stationary phases and preliminary studies on their enantiomer separating ability for chiral protonated primary aralkylamines

  摘要：

  This paper reports the preparation and testing of three new pyridino-18-crown-6 ether-based chiral stationary phases (S,S)-CSP-12, (S,S)-CSP-17 and (S,S)-CSP-20. Secondary amine (S,S)-7 was first transformed to triethoxysilyl derivative (S,S)-11, which contains a urea unit by treating the former with 3-(triethoxysilyl)propyl isocyanate. Next, (S,S)-11 was heated with spherical HPLC quality silica gel in toluene to obtain (S,S)-CSP-12. In order to acetylate the 3-aminopropylsilyl groups bonded to the silica gel during immobilization of the triethoxysilyl derivative (S,S)-11, we pumped acetic anhydride and triethylamine in DMF through the column to give the modified chiral stationary phase (S,S)-CSP-20.Triflate (S,S)-13 was first transformed to a pyridino-18-crown-6 ether derivative (S,S)-15, which contains a 4-(methoxycarbonyl)phenyl substituent at the 4-position of the pyridine ring by a Suzuki carbon-carbon coupling reaction. The hydrolysis of ester (S,S)-15 gave carboxylic acid (S,S)-21. Carboxylic acid (S,S)-21 was reacted with an excess of thionyl chloride to form the appropriate acyl chloride, which was treated with 3-(triethoxysilyl)propylamine in the presence of triethylamine in THF to furnish triethoxysilyl derivative (S,S)-16 containing an amide unit. Triethoxysilyl derivative (S,S)-16 was heated with spherical HPLC quality silica gel in toluene to give the chiral stationary phase (S,S)-CSP-17.The enantiomer separating ability of chiral stationary phases (S,S)-CSP-12, (S,S)-CSP-17 and (S,S)-CSP-20 were tested by using mixtures of enantiomers of 1-(1-naphthyl)ethylamine hydrogen perchlorate (1-NEA), 1-(2-naphthyl)ethylamine (2-NEA), 1-(4-bromophenyl)ethylamine (Br-PEA) and 1-(4-nitrophenyl)ethylamine hydrogen chloride (NO2-PEA). Chiral stationary phase (S,S)-CSP-17 showed the best enantiomer separating ability for the mixtures of enantiomers of amine compounds amongst the pyridino-crown ether-based CSPs ever synthesized. The high enantioselectivity is probably due to the strong pi-pi interaction of the extended pi system of the aryl-substituted pyridine unit. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.04.008
• 作为产物：
  描述：

  (2S,12S)-2,12-dimethyl-4,7,10-trioxatridecane-2,12-diol 在 palladium on activated charcoal 、 氢气 、 sodium hydride 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成 (4S,14S)-(+)-4,14-dimethyl-3,6,9,12,15-pentaoxa-21-azabicyclo[15.3.1]heneicosa-1(21),17,19-trien-19-yl trifluoromethanesulfonate
  参考文献：
  名称：

  含蒽荧光团单元的旋光吡啶并冠醚的合成和对映体识别研究。

  摘要：

  合成了含有蒽荧光团的新型对映体纯的吡啶基-18-冠-6醚基传感器分子。它们对1-苯乙胺高氯酸氢盐（PhEt），1-（1-萘基）乙胺高氯酸氢盐（NapEt），苯甘氨酸甲酯高氯酸氢盐（PhgOMe）和苯丙氨酸甲酯高氯酸氢盐（PheOMe）的对映体识别能力为。使用荧光光谱法在乙腈中检测。传感器分子对NapEt，PhEt和PhgOMe的对映异构体显示出可观的对映异构体识别。发现在大环上含有异丁基的冠醚和NapEt的对映异构体中，对映选择性最高。手性28：562–568，2016。©2016 Wiley Periodicals，Inc.

  DOI：

  10.1002/chir.22614