2,3,4,6-tetra-O-benzoyl-α-D-glucopyranosyl N-phenyltrifluoroacetimidate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,3,4,6-tetra-O-benzoyl-α-D-glucopyranosyl N-phenyltrifluoroacetimidate
• 英文别名: alpha-D-Glucopyranose 1-(N-phenyl-2,2,2-trifluoroacetimidate)2,3,4,6-tetrabenzoate；[(2R,3R,4S,5R,6R)-3,4,5-tribenzoyloxy-6-[N-phenyl-C-(trifluoromethyl)carbonimidoyl]oxyoxan-2-yl]methyl benzoate
• 化学式: C₄₂H₃₂F₃NO₁₀
• 分子量: 767.712
• InChiKey: AMFLBZZPOOKETQ-ZNNRSBSUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.3
• 重原子数：
  56
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  136
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  p-tolyl 2,4-di-O-acetyl-1-thio-α-L-rhamnopyranoside 、 、 2,3,4,6-tetra-O-benzoyl-α-D-glucopyranosyl N-phenyltrifluoroacetimidate 在 三氟甲磺酸三甲基硅酯 、 1-乙基-3-甲基咪唑三氟甲磺酸盐 、 N-碘代丁二酰亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以61%的产率得到
  参考文献：
  名称：

  A sequential one-pot strategy for the synthesis of triterpenoid saponins in ionic liquid [emim][OTf]

  摘要：

  1-乙基-3-甲基咪唑三氟甲磺酸盐([emim][OTf])是一种高效的共溶剂和共催化剂，可与硫代糖苷和三氯乙酰亚胺酯(或N-苯基三氟乙酰亚胺酯)供体在室温下进行一锅式顺序糖基化反应。一锅式糖基化反应对于合成三萜皂苷是高效的，可通过在[emim][OTf]中同时使用N-苯基三氟乙酰亚胺酯供体和2-甲基-5-叔丁基苯基(Mbp)硫代糖苷供体来实现。

  DOI：

  10.1177/1747519819831866
• 作为产物：
  描述：

  2,3,4,6-四-O-苯甲酰基葡萄糖三氯乙酰亚胺酯 在 potassium carbonate 、 palladium dichloride 作用下， 以 水 、 1,2-二氯乙烷 、 丙酮 为溶剂， 反应 29.0h， 生成 2,3,4,6-tetra-O-benzoyl-α-D-glucopyranosyl N-phenyltrifluoroacetimidate
  参考文献：
  名称：

  Regenerative Glycosylation under Nucleophilic Catalysis

  摘要：

  This article describes 3,3-difluoroxindole (HOFox)-mediated glycosylation. The uniqueness of this approach is that both the in situ synthesis of 3,3-difluoro-3H-indol-2-yl (OFox) glycosyl donors and activation thereof can be conducted in a regenerative fashion as is a typical reaction performed under nucleophilic catalysis. Only a catalytic amount of the OFox imidate donor and a Lewis acid activator are present in the reaction medium. The OFox imidate donor is constantly regenerated upon its consumption until glycosyl acceptor has reacted.

  DOI：

  10.1021/ja411746a

文献信息

• OFox imidates as versatile glycosyl donors for chemical glycosylation
  作者：Swati S. Nigudkar、Tinghua Wang、Salvatore G. Pistorio、Jagodige P. Yasomanee、Keith J. Stine、Alexei V. Demchenko

  DOI：10.1039/c6ob02230h

  日期：——

  mediated glycosylations wherein 3,3-difluoro-3H-indol-2-yl (OFox) imidates were found to be key intermediates. Both the in situ synthesis from the corresponding glycosyl bromides and activation of the OFox imidates could be conducted in a regenerative fashion. Herein, we extend this study with the main focus on the synthesis of various OFox imidates and their investigation as glycosyl donors for chemical

  以前，我们交流了3,3-二氟己二酮（HOFox）介导的糖基化作用，其中发现3,3-二氟-3 H-吲哚-2-基（OFox）酰亚胺化是关键中间体。无论是在原位由相应的糖基溴化物和亚胺酸酯OFox活化合成可以在再生的方式进行。在这里，我们扩展了这项研究，主要侧重于各种OFox酰亚胺的合成及其作为化学1,2-顺式和1,2-反式糖基化的糖基供体的研究。
• Glycosyl Trifluoroacetimidates. 2. Synthesis of Dioscin and Xiebai Saponin I
  作者：Biao Yu、Houchao Tao

  DOI：10.1021/jo026103c

  日期：2002.12.1

  Two trisaccharide steroidal saponins, dioscin (1) and Xiebai saponin 1 (2) with various bioactivities, were efficiently synthesized using the newly developed glycosyl N-phenyl trifluoroacetimidates (10-13) as glycosylation donors. Thus, dioscin was synthesized in five steps and a 33% overall yield from diosgenin and glycosyl trifluoroacetimidates (10 and 11). Xiebai saponin I was synthesized in eight steps and a 32% overall yield from laxogenin and glycosyl trifluoroacetimidates (10, 12, and 13), whereupon, the rare steroid laxogenin was prepared from diosgenin in four steps and an overall 69% yield. All the glycosylation reactions involved in the present syntheses demonstrated that glycosyl trifluoroacetimidates were successful donors comparable to the corresponding glycosyl trichloroacetimidates.
• Regenerative Glycosylation under Nucleophilic Catalysis
  作者：Swati S. Nigudkar、Keith J. Stine、Alexei V. Demchenko

  DOI：10.1021/ja411746a

  日期：2014.1.22

  This article describes 3,3-difluoroxindole (HOFox)-mediated glycosylation. The uniqueness of this approach is that both the in situ synthesis of 3,3-difluoro-3H-indol-2-yl (OFox) glycosyl donors and activation thereof can be conducted in a regenerative fashion as is a typical reaction performed under nucleophilic catalysis. Only a catalytic amount of the OFox imidate donor and a Lewis acid activator are present in the reaction medium. The OFox imidate donor is constantly regenerated upon its consumption until glycosyl acceptor has reacted.
• A sequential one-pot strategy for the synthesis of triterpenoid saponins in ionic liquid [emim][OTf]
  作者：Yiming Song、Tiantian Guo、Qingchao Liu、Weiguo Song、Fahui Li

  DOI：10.1177/1747519819831866

  日期：2019.1

  1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][OTf]) is an efficient co-solvent and co-promoter for one-pot sequential glycosylation with the combined use of thioglycosides and trichloroacetimidates (or N-phenyltrifluoroacetimidates) donors at room temperature. One-pot glycosylation is efficient for the synthesis of triterpenoid saponins with the combined use of N-phenyltrifluoroacetimidate donors and 2-methyl-5-tert-butylphenyl (Mbp) thioglycoside donors in [emim][OTf].

  1-乙基-3-甲基咪唑三氟甲磺酸盐([emim][OTf])是一种高效的共溶剂和共催化剂，可与硫代糖苷和三氯乙酰亚胺酯(或N-苯基三氟乙酰亚胺酯)供体在室温下进行一锅式顺序糖基化反应。一锅式糖基化反应对于合成三萜皂苷是高效的，可通过在[emim][OTf]中同时使用N-苯基三氟乙酰亚胺酯供体和2-甲基-5-叔丁基苯基(Mbp)硫代糖苷供体来实现。