methyl 4-O-p-tolylsulfonyl-β-D-xylopyranoside | 84207-38-5

• 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-tolylsulfonyl-β-D-xylopyranoside
• 英文别名: methyl 4-O-tosyl-β-D-xylopyranoside；β-methyl-D-xylose 4-O-tosylate；Me β-D-Xyl 4-O-tosylate；[(3R,4R,5R,6R)-4,5-dihydroxy-6-methoxyoxan-3-yl] 4-methylbenzenesulfonate
• CAS: 84207-38-5
• 化学式: C₁₃H₁₈O₇S
• 分子量: 318.348
• InChiKey: HFEPOKFXXORMAK-YVECIDJPSA-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-tolylsulfonyl-β-D-xylopyranoside 在 吡啶 、 sodium hydroxide 、 lithium aluminium tetrahydride 作用下， 以 乙醇 为溶剂， 反应 2.0h， 生成 methyl 3-deoxy-α-L-threo-pentopyranoside di-O-benzoate
  参考文献：
  名称：

  Utilization of Sugars in Organic Synthesis. XXIII. Part XXII: Lithium Aluminum Hydride Reduction of Glycopyranoside-Monosulfonates: Formation of Branched Furanosides.

  摘要：

  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。

  DOI：

  10.1248/cpb.39.1983
• 作为产物：
  描述：

  methyl 2,3-O-isopropylidene-β-D-xylopyranoside 在 溶剂黄146 作用下， 生成 methyl 4-O-p-tolylsulfonyl-β-D-xylopyranoside
  参考文献：
  名称：

  Selective benzoylation of methyl α- and β-d-xylopyranoside

  摘要：

  DOI：

  10.1016/s0008-6215(00)80551-0

文献信息

• Regioselective Protection of Sugars Catalyzed by Dimethyltin Dichloride
  作者：Yosuke Demizu、Yuki Kubo、Hiroko Miyoshi、Toshihide Maki、Yoshihiro Matsumura、Noriaki Moriyama、Osamu Onomura

  DOI：10.1021/ol802095e

  日期：2008.11.6

  The first catalytic process for protection of hydroxyl groups in sugars has been developed. Highly regioselective protection was accomplished along with high chemical yield. The regioselectivity of the benzoylation was realized as an intrinsic character of sugars based on a stereorelationship among their hydroxyl groups. Furthermore, complete protection of alpha-methyl glucoside and beta-methyl xyloside

  已经开发出用于保护糖中羟基的第一催化方法。高度的区域选择性保护以及高化学产率得以实现。基于糖的羟基之间的立体关系，实现了苯甲酰化的区域选择性是糖的固有特征。此外，完成了对α-甲基葡糖苷和β-甲基木糖苷的完全保护。
• Efficient Synthesis of 4-Amino-4-deoxy-l-arabinose and Spacer-Equipped 4-Amino-4-deoxy-l-arabinopyranosides by Transglycosylation Reactions
  作者：Paul Kosma、Bernhard Müller、Markus Blaukopf、Andreas Hofinger、Alla Zamyatina、Helmut Brade

  DOI：10.1055/s-0030-1258174

  日期：2010.9

  Methyl 4-azido-4-deoxy-β-l-arabinopyranoside has been synthesized in five steps starting from methyl β-d-xylopyranoside in a multigram scale without chromatographic purification in 78% overall yield. The transformation relied on selective tosylation/nosylation at O-4 followed by acylation, SN2 displacement with sodium azide, and subsequent deprotection. The methyl 4-azido-4-deoxy-arabinoside was then

  甲基 4-叠氮基-4-脱氧-β - 1-阿拉伯吡喃糖苷以多克规模从甲基 β- d-吡喃木糖苷开始，分五步合成，无需色谱纯化，总产率为 78%。转化依赖于 O-4 处的选择性甲苯磺酰化/nosylation，然后是酰化，S N2 用叠氮化钠置换，然后去保护。甲基 4-叠氮基-4-脱氧-阿拉伯糖苷然后通过与相应醇的糖基转移以良好的产率和公平的异头选择性转化为烯丙基、丙烯基、ω-溴己基和氯乙氧基乙基间隔糖苷。叠氮基的还原和苷元的进一步转化提供了含 ω-硫醇的间隔衍生物。与马来酰亚胺激活的 BSA 偶联提供了一种有效的免疫原，用于产生与含有 4-氨基-4-脱氧-阿拉伯糖残基的 LPS 核心表位结合的鼠和兔多克隆血清。 氨基阿拉伯糖 - 新糖缀合物 - 转糖基化 - 脂多糖 - 间隔基
• 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。
• 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 monosulfonylation of internal 1,2-diols catalyzed by di-n-butyltin oxide
  作者：Michael J Martinelli、Rajappa Vaidyanathan、Vien Van Khau

  DOI：10.1016/s0040-4039(00)00500-1

  日期：2000.5

  The reaction of internal 1,2-diols with catalytic n-Bu2SnO, p-TsCl (1.05 equiv.) and Et3N (1.1 equiv.) led to selective monotosylation. In the case of cyclic substrates, the cis-1,2-diol moiety appeared best suited for optimal results, supporting the intermediacy of a five-membered chelate. (C) 2000 Elsevier Science Ltd. All rights reserved.