2,5-anhydro-3,6-di-O-methanesulfonyl-L-idose ethylene acetal | 153974-01-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,5-anhydro-3,6-di-O-methanesulfonyl-L-idose ethylene acetal
• 英文别名: [(2S,3R,4S,5R)-5-(1,3-dioxolan-2-yl)-3-hydroxy-4-methylsulfonyloxyoxolan-2-yl]methyl methanesulfonate
• CAS: 153974-01-7
• 化学式: C₁₀H₁₈O₁₀S₂
• 分子量: 362.379
• InChiKey: SHPDTJHOCNWEOS-UYXSQOIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.1
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  151
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,5-anhydro-3,6-di-O-methanesulfonyl-L-idose ethylene acetal 在 吡啶 、 sodium hydroxide 、 sodium hydrogensulfide 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 65.17h， 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
• 作为产物：
  描述：

  乙二醇 、 1,2-O-isopropylidene-3,5,6-O-tri-metahnesulphonyl-α-D-glucofuranose 在 对甲苯磺酸 作用下， 反应 8.5h， 以62%的产率得到2,5-anhydro-3,6-di-O-methanesulfonyl-L-idose ethylene acetal
  参考文献：
  名称：

  An alternative synthesis of (+)-epiallo-muscarine from d-glucose

  摘要：

  DOI：

  10.1016/0008-6215(94)00363-k

文献信息

• Divergent synthesis of two novel muscarine analogues from D-glucose
  作者：Velimir Popsavin、Mirjana Popsavin、Ljubica Radić、Ostoja Berić、Vera Ćirin-Novta

  DOI：10.1016/s0040-4039(99)01952-8

  日期：1999.12

  A divergent synthesis of two new muscarine analogues bearing the (5S)-dioxolanyl isosteric group was achieved starting from d-glucose, enabling access to libraries of potential muscarinic agonists or antagonists. The key step of the synthesis involved a regioselective epoxide ring opening in 2,5:3,4-dianhydro derivatives 5 and 15 with LiAlH4, whereby the natural stereochemistry of (+)-muscarine (1)

  从d-葡萄糖开始，实现了两个新的带有（5 S）-二氧戊环基等规基团的新毒蕈碱类似物的合成，从而可以访问潜在的毒蕈碱激动剂或拮抗剂库。合成的关键步骤涉及在具有LiAlH 4的2,5：3,4-二脱水衍生物5和15中的区域选择性环氧化物开环，从而使（+）-毒蕈碱（1）和（-）-同素异形-有效地建立了毒蕈碱（2）。
• Stereospecific Synthesis of (-)-allo-Muscarine from D-Glucose: Novel Routes to the Key Chiral Synthon
  作者：Velimir Popsavin、Ostoja Beric、Mirjana Popsavin、János Csanádi、Stevan Lajšic、Dušan Miljković

  DOI：10.1135/cccc19970809

  日期：——

  The key chiral synthon in a novel synthesis of (-)-allo-muscarine from D-glucose has been prepared by three independent routes. The most efficient one includes a four-step conversion via the 4-O-benzoyl derivatives of starting 2,5-anhydro-3,5-di-O-methanesulfonyl-L-idose ethylene acetal (2a) into 2,5-anhydro-3,6-dideoxy-L-lyxo-hexose ethylene acetal (4b). The intermediate 4b was efficiently converted into the chiral synthon 2,5-anhydro-4-O-benzoyl-3,6-dideoxy-L-arabino-hexose (4c) by Mitsunobu reaction.

  一项新的从D-葡萄糖合成(-)-allo-肌碱的方法中，关键的手性合成单体已经通过三种独立的途径制备而成。其中最有效的方法包括通过四步反应将起始物2,5-去氧-3,5-二-O-甲磺酰-L-异吡喃乙二醇 (2a)的4-O-苯甲酰衍生物转化为2,5-去氧-3,6-二脱氧-L-lyxo-己糖乙二醇 (4b)。中间体4b经Mitsunobu反应有效地转化为手性合成单体2,5-去氧-4-O-苯甲酰-3,6-二脱氧-L-arabino-己糖 (4c)。
• Stereospecific synthesis of (−)-allo-muscarine from ?-glucose
  作者：V Popsavin

  DOI：10.1016/0008-6215(96)00082-1

  日期：1996.7.19
• An alternative synthesis of (+)-epiallo-muscarine from d-glucose
  作者：Velimir Popsavin、Ostoja Berić、Mirjana Popsavin、Janos Csanádi、Dušan Miljković

  DOI：10.1016/0008-6215(94)00363-k

  日期：1995.4
• 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.