methyl 4-O-p-toluenesulfonyl-α-D-xylopyranoside | 14262-63-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-O-p-toluenesulfonyl-α-D-xylopyranoside
• 英文别名: methyl 4-O-p-tolylsulfonyl-α-D-xylopyranoside；methyl 4-O-tosyl-α-D-xylopyranoside；α-methyl-D-xylose 4-O-tosylate；Me α-D-Xyl 4-O-tosylate；I+/--D-Xylopyranoside, methyl, 4-(4-methylbenzenesulfonate)；[(3R,4R,5R,6S)-4,5-dihydroxy-6-methoxyoxan-3-yl] 4-methylbenzenesulfonate
• CAS: 14262-63-6
• 化学式: C₁₃H₁₈O₇S
• 分子量: 318.348
• InChiKey: HFEPOKFXXORMAK-XQHKEYJVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  111
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 4-O-p-toluenesulfonyl-α-D-xylopyranoside 、 苯甲酰氯 在 吡啶 作用下， 反应 18.0h， 生成 methyl 2,3-di-O-benzoyl-4-O-tosyl-α-D-xylopyranoside
  参考文献：
  名称：

  Investigations into the decomposition of aminoacyl-substituted monosaccharide scaffolds from a drug discovery library

  摘要：

  在酸性条件下，氨基酰取代的d-半乳糖苷支架的分解取决于侧链的长度，并且在C-6位置存在自由羟基时会加速这一过程。在后一种情况下，有证据表明反应是通过N-到O-酰基转移进行的。

  DOI：

  10.1039/c5ob00122f
• 作为产物：
  描述：

  对甲苯磺酰氯 、 甲基-Alpha-D-吡喃木糖 在 4-二甲氨基吡啶 、 二正丁基氧化锡 作用下， 生成 methyl 2-O-p-toluenesulfonyl-α-D-xylopyranoside 、 methyl 4-O-p-toluenesulfonyl-α-D-xylopyranoside
  参考文献：
  名称：

  Utilization of Sugars in Organic Synthesis. XXIV. Regioselective Monotosylation of Non-protected and Partially Protected Glycosides by the Dibutyltin Oxide Method.

  摘要：

  在二丁基锡氧化物活化糖苷后，使用对甲苯磺酰氯和4-二甲氨基吡啶的存在下，对非保护性糖苷进行甲苯磺酰化反应，可得到产量良好的单-O-甲苯磺酸酯。某些糖苷在这种甲苯磺酰化反应中的区域选择性与相应的苯甲酰化反应不同。这种差异的原因基于锡中间体的平衡和甲苯磺酰氯对中间体的动力学攻击。因此，通过将这种方法应用于非保护性和部分保护性糖苷，可以区域选择性地合成各种糖苷单-O-甲苯磺酸酯。

  DOI：

  10.1248/cpb.39.2883

文献信息

• Utilization of Sugars in Organic Synthesis. XXIV. Regioselective Monotosylation of Non-protected and Partially Protected Glycosides by the Dibutyltin Oxide Method.
  作者：Yoshisuke TSUDA、Makoto NISHIMURA、Takuya KOBAYASHI、Yoshiyuki SATO、Kimihiro KANEMITSU

  DOI：10.1248/cpb.39.2883

  日期：——

  Tosylation of non-protected glycopyranosides with p-toluenesulfonyl chloride in the presence of 4-dimethyl-aminopyridine, after activiation of the glycosides by dibutyltin oxide, gave mono-O-tosylates in good yield. The regioselectivity in this tosylation was different from that in the corresponding benzoylation for some glycosides. The reason for this difference is discussed based on an equilibrium of the tin intermediates and kinetic attack of the tosyl chloride on the intermediates. Thus, by application of this tosylation method to non-protected and partially protected glycosides, various glycoside mono-O-tosylates were synthesized regioselectively.

  在二丁基锡氧化物活化糖苷后，使用对甲苯磺酰氯和4-二甲氨基吡啶的存在下，对非保护性糖苷进行甲苯磺酰化反应，可得到产量良好的单-O-甲苯磺酸酯。某些糖苷在这种甲苯磺酰化反应中的区域选择性与相应的苯甲酰化反应不同。这种差异的原因基于锡中间体的平衡和甲苯磺酰氯对中间体的动力学攻击。因此，通过将这种方法应用于非保护性和部分保护性糖苷，可以区域选择性地合成各种糖苷单-O-甲苯磺酸酯。
• Utilization of Sugars in Organic Synthesis. XXIII. Part XXII: Lithium Aluminum Hydride Reduction of Glycopyranoside-Monosulfonates: Formation of Branched Furanosides.
  作者：Yoshisuke TSUDA、Makoto NISHIMURA、Yoko ITO

  DOI：10.1248/cpb.39.1983

  日期：——

  Lithium aluminum hydride reduction of glycopyranoside-monotosylates caused three reactions : (1) stereospecific 1, 2-shift, producing branched furanosides (path A), (2) reductive O-S bond cleavage, producing the original glycosides (path B), and (3) reductive removal of the tosyloxy group, producing deoxyglycosides (path C). The path A reaction was particularly evident for the monotosylates at 2-O, 3-O, and 4-O : for example, methyl 2-O-tosyl-α-D-xylopyranoside gave methyl 2-deoxy-2-C-(hydroxymethyl)-α-D-erythrofuranoside in 60% yield. This reaction opens a new and efficient route to branched glycofuranosides of natural and unnatural type. Stereo-electronic requirements of this reaction in relation to the balance of the other two reactions are discussed.

  乙醇醛糖苷-单甲磺酸酯的锂铝氢还原引发了三种反应：(1) 立体特异性的1,2-移位，生成分支呋喃糖苷(路径A)，(2) 还原性O-S键断裂，生成原始糖苷(路径B)，以及(3) 甲磺酰氧基的还原性移除，生成去氧糖苷(路径C)。在2-O、3-O和4-O位置的单甲磺酸酯中，路径A反应尤为显著；例如，甲基2-O-甲磺酰-α-D-木糖吡喃糖苷以60%的产率转化为甲基2-脱氧-2-C-(羟甲基)-α-D-赤藓呋喃糖苷。该反应为天然与非天然型分支糖呋喃糖苷的合成开辟了一条新颖高效的途径。本反应的立体电子学需求与其余两种反应的平衡关系在此讨论。
• Catalytic Regioselective Sulfonylation of α-Chelatable Alcohols:  Scope and Mechanistic Insight
  作者：Michael J. Martinelli、Rajappa Vaidyanathan、Joseph M. Pawlak、Naresh K. Nayyar、Ulhas P. Dhokte、Christopher W. Doecke、Lisa M. H. Zollars、Eric D. Moher、Vien Van Khau、Berta Košmrlj

  DOI：10.1021/ja016031r

  日期：2002.4.1

  This paper describes a convenient protocol for the regioselective sulfonylation of alpha-chelatable alcohols. Typically, the reaction of alpha-heterosubstituted alcohols with 1 equiv of p-TsCl and 1 equiv of Et3N in the presence of 2 mol % of Bu2SnO leads to rapid, regioselective, and exclusive monotosylation. The pKa of the amine was correlated to the reaction rate. A plausible mechanism for this reaction has been proposed on the basis of Sn-119 NMR studies.
• Selective benzoylation of methyl α- and β-d-xylopyranoside
  作者：Yôtaro Kondo

  DOI：10.1016/s0008-6215(00)80551-0

  日期：1982.9
• Partial sulfonylation of methyl α- and β-d-xylopyranoside
  作者：Yôtaro Kondo

  DOI：10.1016/0008-6215(82)84018-4

  日期：1982.12