2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl thiocyanate | 158419-88-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl thiocyanate
• 英文别名: [(2R,3R,4S,5R,6S)-3,4,5-tribenzoyloxy-6-thiocyanatooxan-2-yl]methyl benzoate
• CAS: 158419-88-6
• 化学式: C₃₅H₂₇NO₉S
• 分子量: 637.667
• InChiKey: FPAJLUHHLVBFBZ-HOUGBNEZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.2
• 重原子数：
  46
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  164
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl thiocyanate 在 甲酸 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.67h， 生成 S-trifluoromethyl 1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  An unprecedented access to trifluoromethylthiosugar derivatives from thiocyanate precursors upon treatment with trifluoromethyltrimethylsilane

  摘要：

  Upon treatment with trifluoromethyltrimethylsilane (2 equiv) in oxolane at 0 degrees C in the presence of a catalytic amount of tetra-n-butylammonium fluoride (0.2 equiv), various protected sugar derivatives having a thiocyanato group attached to different positions (anomeric, secondary, primary) were converted into the corresponding trifluoromethylthio derivatives. Under these conditions, highly selective, albeit partial transformations of primary and secondary thiocyanate groups were achieved while a decreased selectivity was observed when the reaction involved a more reactive anomeric thiocyanate group. However, in this case, lowering the reaction temperature led to enhanced selectivity and higher isolated yields. The isopropylidene and benzoyl protecting groups in the resulting trifluoromethylthiosugar derivatives were removed by standard methods to afford the corresponding free trifluoromethylthio derivatives, generally in high yield and as crystalline solids. Hence, this method opens a practical access to new trifluoromethylthiosugars obtained under smooth conditions as protected or unprotected derivatives. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(98)00289-4
• 作为产物：
  描述：

  2,3,4,6-tetra-O-benzoylglucosyl bromide 、 potassium thioacyanate 在 18-冠醚-6 作用下， 以 丙酮 为溶剂， 反应 7.0h， 以83%的产率得到2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl thiocyanate
  参考文献：
  名称：

  糖硫氰酸盐与格氏试剂的反应。硫糖苷的新合成。

  摘要：

  在-40℃下，具有被乙酰基或苯甲酰基保护的羟基的糖基硫氰酸氰酸酯易于与格氏试剂反应，以高收率得到相应的烷基或芳基硫代糖苷。在相似条件下形成在其他位置具有SCN基团的单糖衍生物可形成硫醚。轴向硫氰酸盐不反应。升高的温度引起副反应，导致硫醇。

  DOI：

  10.1016/s0040-4020(01)87009-5

文献信息

• The Michaelis–Arbuzov rearrangement of anomeric thiocyanates: synthesis and application of S-glycosyl thiophosphates, thiophosphonates and thiophosphinates as glycosyl donors
  作者：Marta Piekutowska、Zbigniew Pakulski

  DOI：10.1016/j.tetlet.2007.09.162

  日期：2007.11

  Reaction of anomeric thiocyanates with triethyl phosphite, dimethyl phenylphosphonite and methyl diphenylphosphinite afforded the corresponding S-glycosyl thiophosphates, thiophosphonates and thiophosphinates in good yields. These derivatives were applied as glycosyl donors in the synthesis of benzyl glycosides and disaccharides with excellent stereoselectivity.

  异头硫氰酸酯与亚磷酸三乙酯，二甲基苯基膦酸酯和甲基二苯基次膦酸酯的反应以良好的产率得到了相应的S-糖基硫代磷酸酯，硫代膦酸酯和硫代膦酸酯。这些衍生物被用作糖基供体，以优异的立体选择性合成苄基糖苷和二糖。
• Glycosyl Alkoxythioimidates as Complementary Building Blocks for Chemical Glycosylation
  作者：Sneha C. Ranade、Sophon Kaeothip、Alexei V. Demchenko

  DOI：10.1021/ol1023079

  日期：2010.12.17

  It is reported that S-glycosyl O-methyl phenylcarbamothioates (SNea carbamothioates) have a fully orthogonal character in comparison to S-benzoxazolyl (SBox) glycosides. This complete orthogonality was revealed by performing competitive glycosylation experiments in the presence of various promoters. The results obtained indicate that SNea carbamothioates have a very similar reactivity profile to that of glycosyl thiocyanates, yet are significantly more stable and tolerate selected protecting group manipulations. These features make the SNea carbamothioates new promising building blocks for further utilization in
• Influence of bromide ions on the synthesis of anomeric thiocyanates
  作者：Piotr Cmoch、Zbigniew Pakulski

  DOI：10.1016/j.tet.2012.06.068

  日期：2012.9

  The synthesis of anomeric thiocyanates with the alpha- and beta-configuration is described. Reactions performed under standard conditions afforded the 1,2-trans derivatives as the main products, whereas in the presence of the quaternary ammonium salts, the 1,2-cis-thiocyanates were formed preferentially. The strong influence of the bromide ions on the distribution of the products is discussed. (C) 2012 Elsevier Ltd. All rights reserved.
• On Orthogonal and Selective Activation of Glycosyl Thioimidates and Thioglycosides: Application to Oligosaccharide Assembly
  作者：Sophon Kaeothip、Alexei V. Demchenko

  DOI：10.1021/jo201117s

  日期：2011.9.16

  Discrimination among S-thiazolinyl (STaz), S-benzoxazolyl (SBox), and S-ethyl anomeric leaving groups was achieved by fine-tuning activation conditions. Preferential glycosidation of a certain leaving group is determined neither by the strength of the activating reagent nor by the stability of the leaving group itself; instead, the type of activation plays the key role. The activation conditions established herein were applied to a sequential five-step synthesis of a hexasaccharide using six monosaccharide building blocks equipped with six different leaving groups.
• Studies into the preparation of 1-deoxy-1-thiocyanato-d-glycopyranosyl cyanides and the anomeric effect of the thiocyanate group
  作者：László Somsák、Katalin Czifrák、Tamás Deim、László Szilágyi、Attila Bényei

  DOI：10.1016/s0957-4166(01)00112-4

  日期：2001.4

  The reaction of per-O-acetylated 1-bromo-1-deoxy-alpha -D-arabinopyranosyl cyanide with thiocyanate ions gave the corresponding 1-deoxy-1-thiocyanato-alpha- and beta -D-arabinopyranosyl cyanides. In the reaction of the per-O-acetylated 1-bromo-1-deoxy-beta -D-xylopyranosyl cyanide and its per-O-benzoylated beta -D-glucopyranosyl analogue the corresponding 2-hydroxy-glycal esters formed in addition to the anomeric pair of thiocyanato-cyanides. The formation of 2,3,4,6-tetra-O-benzoyl-alpha -D-glycopyranosyl thiocyanate was demonstrated in the reaction of benzobromoglucose with thiocyanate ions. The equilibrium constant between 2,3,4,6-tetra-O-acetyl-1-deoxyl-1-thiocyanato-alpha- and beta -D-galactopyranosyl cyanides was determined. Based on this value, the equilibrium ratio for the 2.3.4,6-tetra-O-acetyl-alpha- and beta -D-galactopyranosyl thiocyanates was calculated to be 94:6, and the anomeric effect of the SCN group was estimated to exceed 3 kcal/mol. X-Ray crystallographic data support endo- and exo-anomeric effects of the SCN moiety. (C) 2001 Elsevier Science Ltd. All rights reserved.