[(1R,3S,4S,7R)-3-(1,3-dioxolan-2-yl)-2-oxa-5-thiabicyclo[2.2.1]heptan-7-yl] trifluoromethanesulfonate | 226710-00-5

• 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: [(1R,3S,4S,7R)-3-(1,3-dioxolan-2-yl)-2-oxa-5-thiabicyclo[2.2.1]heptan-7-yl] trifluoromethanesulfonate
• CAS: 226710-00-5
• 化学式: C₉H₁₁F₃O₆S₂
• 分子量: 336.31
• InChiKey: DWNBWQVCZFTKTC-BDVNFPICSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  [(1R,3S,4S,7R)-3-(1,3-dioxolan-2-yl)-2-oxa-5-thiabicyclo[2.2.1]heptan-7-yl] trifluoromethanesulfonate 在 镍 氢气 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 25.0h， 生成 Benzoic acid (1R,6S,7R,9S)-9-methyl-2,5,8-trioxa-bicyclo[5.2.1]dec-6-yl ester
  参考文献：
  名称：

  Dioxolane acetal ring expansion during a sugar triflate displacement. Synthesis and assignment of diastereoisomer configuration of novel 9-crown-3 ether derivatives

  摘要：

  Treatment of 2,5:3,6-dianhydro-6-thio-4-O-trifluoromethanesulfonyl-L-talose ethylene acetal (5) with lithium benzoate in boiling DMF unexpectedly gave the 9-crown-3 ether derivatives 7 and 8 instead of the substitution product 6. The mechanism of the process presumably involved neighbouring group participation of the dioxolane acetal function. H-1 NMR and molecular mechanics calculations (MM3) provided the assignment of stereoisomer configuration since the results of semi-empirical PM3 calculations on postulated oxonium-ion intermediates reasonably explained the high stereoselectivity of the process. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00492-x
• 作为产物：
  描述：

  2.5-anhydro-4-O-benzoyl-3,6-thioanhydro-L-talose ethylene acetal 在 吡啶 、 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.17h， 生成 [(1R,3S,4S,7R)-3-(1,3-dioxolan-2-yl)-2-oxa-5-thiabicyclo[2.2.1]heptan-7-yl] trifluoromethanesulfonate
  参考文献：
  名称：

  Dioxolane acetal ring expansion during a sugar triflate displacement. Synthesis and assignment of diastereoisomer configuration of novel 9-crown-3 ether derivatives

  摘要：

  Treatment of 2,5:3,6-dianhydro-6-thio-4-O-trifluoromethanesulfonyl-L-talose ethylene acetal (5) with lithium benzoate in boiling DMF unexpectedly gave the 9-crown-3 ether derivatives 7 and 8 instead of the substitution product 6. The mechanism of the process presumably involved neighbouring group participation of the dioxolane acetal function. H-1 NMR and molecular mechanics calculations (MM3) provided the assignment of stereoisomer configuration since the results of semi-empirical PM3 calculations on postulated oxonium-ion intermediates reasonably explained the high stereoselectivity of the process. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00492-x

文献信息

• Dioxolane acetal ring expansion during a sugar triflate displacement. Synthesis and assignment of diastereoisomer configuration of novel 9-crown-3 ether derivatives
  作者：Velimir Popsavin、Ostoja Berić、Mirjana Popsavin、János Csanádi、Djura Vujić、Richard Hrabal

  DOI：10.1016/s0040-4039(99)00492-x

  日期：1999.4

  Treatment of 2,5:3,6-dianhydro-6-thio-4-O-trifluoromethanesulfonyl-L-talose ethylene acetal (5) with lithium benzoate in boiling DMF unexpectedly gave the 9-crown-3 ether derivatives 7 and 8 instead of the substitution product 6. The mechanism of the process presumably involved neighbouring group participation of the dioxolane acetal function. H-1 NMR and molecular mechanics calculations (MM3) provided the assignment of stereoisomer configuration since the results of semi-empirical PM3 calculations on postulated oxonium-ion intermediates reasonably explained the high stereoselectivity of the process. (C) 1999 Elsevier Science Ltd. All rights reserved.