p-tolyl 4,6-di-O-acetyl-2-deoxy-2-N-acetyl-1-thio-β-D-glucopyranosid[2,3-d]-1,3-oxazolidin-2-one | 853059-00-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-tolyl 4,6-di-O-acetyl-2-deoxy-2-N-acetyl-1-thio-β-D-glucopyranosid[2,3-d]-1,3-oxazolidin-2-one
• 英文别名: p-methylphenyl 2-N-acetyl-4,6-di-O-acetyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside；[(3aR,4S,6R,7S,7aR)-3-acetyl-7-acetyloxy-4-(4-methylphenyl)sulfanyl-2-oxo-4,6,7,7a-tetrahydro-3aH-pyrano[3,4-d][1,3]oxazol-6-yl]methyl acetate
• CAS: 853059-00-4
• 化学式: C₂₀H₂₃NO₈S
• 分子量: 437.471
• InChiKey: GWNJPNGUSXDTTN-NNIGNNQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  134
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  p-tolyl 4,6-di-O-acetyl-2-deoxy-2-N-acetyl-1-thio-β-D-glucopyranosid[2,3-d]-1,3-oxazolidin-2-one 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 methyl 2-N-acetyl-4,6-di-O-acetyl-2,3-N,O-carbonyl-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Electrochemical generation of 2,3-oxazolidinone glycosyl triflates as an intermediate for stereoselective glycosylation

  摘要：

  用低温电化学氧化从硫代糖苷生成带有2,3-噁唑啉醇保护基的糖基三氟甲磺酸酯。糖基三氟甲磺酸酯与醇在低温下反应，选择性地形成相应的糖苷β-选择性产物。然而，在高温反应条件下，在无碱存在的情况下观察到α-选择性。原位生成的三氟甲磺酸促进β-产物向α-产物的异构化。

  DOI：

  10.3762/bjoc.8.52
• 作为产物：
  描述：

  p-tolyl 4,6-di-O-acetyl-2-deoxy-1-thio-β-D-glucopyranosid[2,3-d]-1,3-oxazolidin-2-one 、 乙酸酐 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 2.0h， 以99%的产率得到p-tolyl 4,6-di-O-acetyl-2-deoxy-2-N-acetyl-1-thio-β-D-glucopyranosid[2,3-d]-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Factors Affecting Stereocontrol during Glycosidation of 2,3-Oxazolidinone-Protected 1-Tolylthio-N-acetyl-d-glucosamine

  摘要：

  It is demonstrated that a ring-fused 2,3-oxazolidinone-protected derivative of 1-tolylthio-N-acetyl-D-glucosamine undergoes high-yield glycosidation under mild donor activation conditions. Stereoselective formation of alpha-linked or beta-linked glycosides is dependent on reactivity of acceptor alcohols, where rate of glycosidation correlates to stereochemical outcome. Evidence for the role of glycosyl triflate intermediates and the N-acetyl substituent of the 2N,3O-oxazolidinone ring in stereochemical control is presented.

  DOI：

  10.1021/jo047812o

文献信息

• Pre-activation protocol leading to highly stereoselectivity-controllable glycosylations of oxazolidinone protected glucosamines
  作者：Yiqun Geng、Li-He Zhang、Xin-Shan Ye

  DOI：10.1039/b712591g

  日期：——

  Under pre-activation glycosylation conditions, the 4,6-di-O-acetyl-N-acetyloxazolidinone protected donor afforded either excellent β- or α-stereoselectivity simply by means of the addition of hindered base TTBP or the absence of base, leading to the controllable stereochemistry of coupling reactions.

  在预活化糖基化条件下，4,6-二-O-乙酰基-N-乙酰基噁唑烷酮保护的供体通过添加障碍基碱TTBP或不添加碱，获得了优异的β-或α-立体选择性，从而实现了偶联反应的可控立体化学。
• O,O-Dimethylthiophosphonosulfenyl bromide-silver triflate: a new powerful promoter system for the preactivation of thioglycosides
  作者：Peng Peng、Xin-Shan Ye

  DOI：10.1039/c0ob00380h

  日期：——

  O,O-Dimethylthiophosphonosulfenyl bromide (DMTPSB) in combination with silver triflate provides a powerful thiophilic promoter system. Both “armed” and “disarmed” thioglycoside glycosyl donors can be activated to form glycosidic linkages efficiently by the pre-activation protocol. The usefulness of this new promoter is illustrated by a successful iterative one-pot oligosaccharide assembly.

  O，O-二甲基硫代膦酰基磺酰基溴（DMTPSB）与三氟甲磺酸银提供了强大的亲硫性助催化剂系统。可以通过预激活方案将“武装的”和“解除武装的”硫代糖苷糖基供体两者活化，以有效地形成糖苷键。一个成功的迭代一锅寡糖组装说明了这种新启动子的有用性。
• Additive-Controlled Stereoselective Glycosylations of Oxazolidinone-Protected Glucosamine and Galactosamine Thioglycoside Donors Based on Preactivation Protocol
  作者：Xin-Shan Ye、Yiqun Geng

  DOI：10.1055/s-0030-1258557

  日期：2010.10

  Based on a pre-activation protocol, the stereoselectivity of oxazolidinone-protected amino sugar thioglycoside donors towards glycosylations can be controlled by additives. Either α- or β-selectivity could be obtained by changing additives. 2,4,6-Tri-tert-butylpyrimidine (TTBP) was the best β-directing additive, while thiophene worked as the best α-directing additive. The bifunctional additives such as tetrabutyl ammonium iodide (TBAI) afforded either α- or β-selectivity depending on the amount added. Poor α-­selectivity of some glycosylations without any additives was greatly improved by adding TBAI or thiophene.

  根据预激活方案，可通过添加剂控制噁唑烷酮保护的氨基糖硫代糖苷给体对糖基化的立体选择性。通过改变添加剂可获得δ-或δ-选择性。2,4,6-三叔丁基嘧啶（TTBP）是最好的δ-定向添加剂，而噻吩则是最好的δ-定向添加剂。双功能添加剂，如四丁基碘化铵（TBAI），根据添加量的不同，可提供δ-或δ-选择性。添加 TBAI 或噻吩后，一些未添加任何添加剂的糖基化反应的δ-选择性大大提高。
• Additive-controlled stereoselective glycosylations of 2,3-oxazolidinone protected glucosamine or galactosamine thioglycoside donors with phenols based on preactivation protocol
  作者：Qi Qin、De-Cai Xiong、Xin-Shan Ye

  DOI：10.1016/j.carres.2014.07.004

  日期：2015.2

  Stereo-controllable glycosylation reactions of 2,3-oxazolidinone protected glucosamine thioglycoside donor with different phenol acceptors based on preactivation protocol, are described. It was found that BF3.Et2O worked as alpha-directing additive, while TTBP acted as beta-directing additive. Simply by altering additives, either alpha-aryl glycosides or beta-aryl glycosides were achieved in a stereoselective manner. The additives were also applied to the stereoselective glycosylation reactions of 2,3-oxazolidinone protected galactosamine donor with phenol substrates. (C) 2014 Elsevier Ltd. All rights reserved.