N'-(β-D-glucopyranosyl)-p-toluenesulfonohydrazide

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N'-(β-D-glucopyranosyl)-p-toluenesulfonohydrazide
• 英文别名: 4-methyl-N'-[(2R,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]benzenesulfonohydrazide
• 化学式: C₁₃H₂₀N₂O₇S
• 分子量: 348.377
• InChiKey: QFTMHKHHOVFAMI-UJPOAAIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  157
• 氢给体数：
  6
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  N'-(β-D-glucopyranosyl)-p-toluenesulfonohydrazide 在 N-溴代丁二酰亚胺(NBS) 、 四丁基氯化铵 作用下， 以 丙酮 为溶剂， 生成 α-glucosyl chloride
  参考文献：
  名称：

  Protecting-group-free O-glysosidation using p-toluenesulfonohydrazide and glycosyl chloride donors

  摘要：

  A range of N '-glycosylsulfonohydrazides (GSHs) display good reactivity but poor stereoselectivity in protecting- group-free O-glycosidations when a moderate excess of the model acceptor n-decanol is employed. This stable, readily-accessed class of donor may be more tractable for the glycosylation of non-volatile acceptors than Fischer's glycosidation conditions. It is possible to generate unprotected glycosyl chlorides from GSHs in situ. In an effort to find conditions to improve glycosidation stereoselectivity, methanolysis of unprotected glucosyl chloride under halide-ion exchange conditions was examined. Relative to its tetra-O-benzyl analogue, this donor displays moderate, inverted stereoselectivity and a significantly faster reaction rate. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2013.08.019
• 作为产物：
  描述：

  葡萄糖 、 对甲苯磺酰肼 以 水 、 N,N-二甲基甲酰胺 为溶剂， 以90%的产率得到N'-(β-D-glucopyranosyl)-p-toluenesulfonohydrazide
  参考文献：
  名称：

  Protecting-Group-Free Synthesis of Glycosyl 1–Phosphates

  摘要：

  Glycosyl 1-phosphates enriched in the alpha-anomer are obtained without the use of protecting groups in two steps starting from the free hemiacetal. Condensation of free hemiacetals with toluenesulfonylhydrazide yields a range of glycosylsulfonohydrazide donors which can be oxidized using cupric chloride in the presence of phosphoric acid and the coordinating additive 2-methyl-2-oxazoline to give useful yields of the fully deprotected glycosyl 1-phosphates.

  DOI：

  10.1021/ol3019083
• 作为试剂：
  描述：

  1-甲基吲哚 、 2-环戊烯酮 在 N'-(β-D-glucopyranosyl)-p-toluenesulfonohydrazide 作用下， 以 水 为溶剂， 反应 12.0h， 以89%的产率得到3-(3-(1-methylindolyl))cyclopentanone
  参考文献：
  名称：

  Carbohydrate-Based Tolylsulfonyl Hydrazines: Effective Catalysts for Michael Addition of Indoles to Electron-Deficient Olefins in Water

  摘要：

  首次使用基于碳水化合物的托尔烷基磺酰肼催化吲哚与电子缺乏的烯烃在水相介质中进行迈克尔反应，顺利获得3-取代的吲哚衍生物，产率良好至优异，反应在室温下进行。

  DOI：

  10.1055/s-2008-1072735

文献信息

• Stability studies of hydrazide and hydroxylamine-based glycoconjugates in aqueous solution
  作者：Anna V. Gudmundsdottir、Caroline E. Paul、Mark Nitz

  DOI：10.1016/j.carres.2008.11.007

  日期：2009.2

  Glycoconjugates can be readily formed by the condensation of a free-reducing terminus and a strong alpha-effect nucleophile, such as a hydrazide or a hydroxylamine. Further characterization of a series of glycoconjugates formed from xylose, glucose and N-acetylglucosamine, and either p-toluenesulfonyl hydrazide or an N-methylhydroxylamine, was carried out to gain insight into the optimal conditions for the formation of these useful conjugates, and their stability. Their apparent association constants (974 M-1) at pH 4.5; as well, as rate constants for hydrolysis, at pH 4.0, 5.0 and 6.0 (37 degrees C), were determined. The half-lives of the conjugates varied between 3 h and 300 days, All the compounds were increasingly stable as the pH approached neutrality. Conjugate hydrolysis rates mirrored those found for O-glycoside hydrolysis where conjugates formed from electron-rich monosaccharides hydrolyzed more rapidly. (C) 2008 Elsevier Ltd. All rights reserved
• Protecting-Group-Free Synthesis of Glycosyl 1–Phosphates
  作者：Landon John G. Edgar、Somnath Dasgupta、Mark Nitz

  DOI：10.1021/ol3019083

  日期：2012.8.17

  Glycosyl 1-phosphates enriched in the alpha-anomer are obtained without the use of protecting groups in two steps starting from the free hemiacetal. Condensation of free hemiacetals with toluenesulfonylhydrazide yields a range of glycosylsulfonohydrazide donors which can be oxidized using cupric chloride in the presence of phosphoric acid and the coordinating additive 2-methyl-2-oxazoline to give useful yields of the fully deprotected glycosyl 1-phosphates.
• Protecting-group-free O-glysosidation using p-toluenesulfonohydrazide and glycosyl chloride donors
  作者：Rohan J. Williams、Caroline E. Paul、Mark Nitz

  DOI：10.1016/j.carres.2013.08.019

  日期：2014.3

  A range of N '-glycosylsulfonohydrazides (GSHs) display good reactivity but poor stereoselectivity in protecting- group-free O-glycosidations when a moderate excess of the model acceptor n-decanol is employed. This stable, readily-accessed class of donor may be more tractable for the glycosylation of non-volatile acceptors than Fischer's glycosidation conditions. It is possible to generate unprotected glycosyl chlorides from GSHs in situ. In an effort to find conditions to improve glycosidation stereoselectivity, methanolysis of unprotected glucosyl chloride under halide-ion exchange conditions was examined. Relative to its tetra-O-benzyl analogue, this donor displays moderate, inverted stereoselectivity and a significantly faster reaction rate. (C) 2013 Elsevier Ltd. All rights reserved.