2-thiazolinyl 2-O-benzyl-3,4,6-tri-O-acetyl-1-thio-β-D-glucopyranoside | 744246-08-0

• 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-thiazolinyl 2-O-benzyl-3,4,6-tri-O-acetyl-1-thio-β-D-glucopyranoside
• 英文别名: 2-thiazolinyl 3,4,6-tri-O-acetyl-2-O-benzyl-1-thio-β-D-glucopyranoside；[(2R,3R,4S,5R,6S)-3,4-diacetyloxy-6-(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)-5-phenylmethoxyoxan-2-yl]methyl acetate
• CAS: 744246-08-0
• 化学式: C₂₂H₂₇NO₈S₂
• 分子量: 497.59
• InChiKey: SALALXFPVUYYGV-ADAARDCZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  33
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  160
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2-thiazolinyl 2-O-benzyl-3,4,6-tri-O-acetyl-1-thio-β-D-glucopyranoside 在 甲醇 、 sodium methylate 作用下， 反应 2.0h， 生成
  参考文献：
  名称：

  How the Arming Participating Moieties can Broaden the Scope of Chemoselective Oligosaccharide Synthesis by Allowing the Inverse Armed−Disarmed Approach

  摘要：

  A new method for stereocontrolled glycosylation and chemoselective oligosaccharide synthesis has been developed. It has been determined that complete 1,2-trans selectivity can be achieved with the use of a 2-O-picolyl moiety, a novel neighboring group that is capable of efficient participation via a six-membered intermediate. The application of the picolyl concept to glycosidations of thioimidoyl, thioglycosyl, and trichloroacetimidoyl glycosyl donors is demonstrated. The picolyl moiety also retains the glycosyl donor in the armed state, as opposed to conventional acyl participating moieties. We name this new approach the "inverse armed-disarmed" strategy, because it allows for the chemoselective introduction of a 1,2-trans glycosidic linkage prior to other linkages. In the context of the oligosaccharide synthesis, the strategy provides trans-trans and trans-cis patterned oligosaccharides as opposed to classic Fraser-Reid's armed-disarmed approach leading to cis-trans and cis-cis linkages.

  DOI：

  10.1021/jo801551r
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-2-O-benzyl-α-D-glucopyranosyl bromide 、 sodium 2-mercaptothiazolinate 在 15-冠醚-5 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以46%的产率得到2-thiazolinyl 2-O-benzyl-3,4,6-tri-O-acetyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  高效，通用和稳定：噻唑基硫代糖苷作为糖基供体。

  摘要：

  DOI：

  10.1002/anie.200454047

文献信息

• S-Thiazolinyl (STaz) Glycosides as Versatile Building Blocks for Convergent Selective, Chemoselective, and Orthogonal Oligosaccharide Synthesis
  作者：Papapida Pornsuriyasak、Alexei V. Demchenko

  DOI：10.1002/chem.200600262

  日期：2006.8.25

  In the aim of developing new procedures for efficient oligosaccharide assembly, a range of S-thiazolinyl (STaz) glycosides have been synthesized. These novel derivatives were evaluated against a variety of reaction conditions and were shown to be capable of being chemoselectively activated in the armed-disarmed fashion. Moreover, the S-thiazolinyl moiety exhibited a remarkable propensity for selective

  为了开发有效寡糖组装的新方法，已合成了一系列S-噻唑啉基（STaz）糖苷。这些新颖的衍生物针对各种反应条件进行了评估，并显示出能够以武装-解除武装的方式进行化学选择性活化。此外，与其他常见的离去基团相比，S-噻唑啉基部分显示出显着的选择性活化倾向。相反，可以在STaz部分上选择性激活各种离去基团，从而允许STaz / S-乙基和STaz / S-苯基正交方法。为了证明新型STaz衍生物的多功能性，已经以收敛的选择性，正交和化学选择性方式合成了许多寡糖靶标。
• Silver(I) tetrafluoroborate as a potent promoter for chemical glycosylation
  作者：Sophon Kaeothip、Papapida Pornsuriyasak、Alexei V. Demchenko

  DOI：10.1016/j.tetlet.2007.12.105

  日期：2008.2

  promoter for the activation of various glycosyl donors including glycosyl halides, trichloroacetimidates, thioimidates, etc. Easy handling and no requirement for azeotropic dehydration prior to application makes AgBF(4) especially beneficial in comparison to the commonly used AgOTf. Selective activation of glycosyl halides or thioimidates over thioglycosides or n-pentenyl glycosides, including simple

  我们已经确定四氟硼酸银 (AgBF(4)) 是激活各种糖基供体的极好促进剂，包括糖基卤化物、三氯乙酰亚胺酸盐、硫代亚胺酸盐等。 易于处理且在应用前不需要共沸脱水使 AgBF(4) 特别有益与常用的 AgOTf 相比。糖基卤化物或硫代亚胺酯相对于硫代糖苷或正戊烯基糖苷的选择性活化，包括简单的顺序一锅合成，也已被证明。通过将这些中间体转化为各种其他类别的糖基供体，进一步探索了糖基硫代亚胺酯的多功能性。
• Synthesis, characterization and reactivity of carbohydrate platinum(iv) complexes with thioglycoside ligands
  作者：Cornelia Vetter、Papapida Pornsuriyasak、Jürgen Schmidt、Nigam P. Rath、Tobias Rüffer、Alexei V. Demchenko、Dirk Steinborn

  DOI：10.1039/b927058b

  日期：——

  fac-[PtMe3(4,4′-R2bpy)(Me2CO)][BF4] (R = H, 1a; tBu, 1b) and fac-[PtMe3(OAc-κ2O,O′)(Me2CO)] (2), respectively, with thioglycosides containing thioethyl (ch-SEt) and thioimidate (ch-STaz, Taz = thiazoline-2-yl) anomeric groups led to the formation of the carbohydrate platinum(IV) complexes fac-[PtMe3(4,4′-R2bpy)(ch*)][BF4] (ch* = ch-SEt, 8–14; ch-STaz, 15–23) and fac-[PtMe3(OAc-κ2O,O′)(ch*)] (ch* = ch-SEt, 24–28;

  的反应FAC - [PTME 3（4,4'-R 2联吡啶）（ME 2 CO）] [BF 4 ]（R =H, 1a ;Ť卜, 1b ) 和FAc -[PTMe 3 (OAc-κ 2 O , O ')(Me 2 CO)]( 2 )、分别含硫糖苷硫乙基 (ch-SEt） 和 硫代亚氨酸盐 (ch-STAz, 塔兹 = 噻唑啉-2-基) 异头基团导致碳水化合物铂 ( IV ) 复合物FAc -[PTMe 3 (4,4'-R 2 bpy)(ch*)][BF 4 ] (ch* = ch-SEt, 8–14 ; ch-STAz, 15–23 ) 和FAc -[PTMe 3 (OAc-κ 2 O , O ')(ch*)](ch* = ch-SEt, 24–28 ; ch-STaz = 29–35 )，分别。核磁共振 ( 1 H,13 ℃, 195铂) 光谱研究和19 (ch-STaz =2-噻唑啉基 2,3
• On the stereoselectivity of glycosidation of thiocyanates, thioimidates, and thioglycosides
  作者：Sophon Kaeothip、Steven J. Akins、Alexei V. Demchenko

  DOI：10.1016/j.carres.2010.08.003

  日期：2010.10

  Comparative side-by-side glycosylation studies demonstrated that glycosyl thiocyanates, thioimidates, and thioglycosides provide comparative stereoselectivities in glycosylations. Very high alpha-stereoselectivity that was previously recorded for glycosyl thiocyanates can be achieved, but only if glycosyl acceptors are equipped with electron-withdrawing acyl substituents. Partially benzylated glycosyl acceptors provided relatively modest stereoselectivity, which was on a par with other common glycosyl donors. Accordingly, thioimidates and thioglycosides showed high stereoselectivity similarly to that of thiocyanates with different classes of acylated primary and secondary glycosyl acceptors. (C) 2010 Elsevier Ltd. All rights reserved.