methyl 2,6-di-O-tert-butyldimethylsilyl-α-D-galactopyranoside | 116144-17-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,6-di-O-tert-butyldimethylsilyl-α-D-galactopyranoside
• 英文别名: 2,6-O-bis(tert-butyldimethylsilanyl)-1-O-methyl-α-D-galactopyranoside；methyl α-D-galactopyranoside 2,6-di-tert-butyldimethylsilyl ether；TBDMS(-2)[TBDMS(-6)]a-Gal1Me；(2R,3R,4S,5R,6S)-5-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-methoxyoxane-3,4-diol
• CAS: 116144-17-3
• 化学式: C₁₉H₄₂O₆Si₂
• 分子量: 422.71
• InChiKey: IYOLDHREOIQTQU-HMDCTGQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.49
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2,6-di-O-tert-butyldimethylsilyl-α-D-galactopyranoside 在 甲醇 、 copper(ll) sulfate pentahydrate 、 sodium hydride 、 sodium ascorbate 、 乙酰氯 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.96h， 生成 3,4-di-O-(1-coumarinyltriazol-4-yl)-1-O-methyl-α-D-galactopyranoside
  参考文献：
  名称：

  Creation of 3,4-bis-triazolocoumarin–sugar conjugates via flourogenic dual click chemistry and their quenching specificity with silver(I) in aqueous media

  摘要：

  Fluorogenic click chemistry has recently emerged as an ingenious and powerful tool toward numerous biochemical purposes. We describe herein the use of dual click chemistry toward the fluorescence restoration of a fluorogenic coumarin on epimeric dipropargyl sugar scaffolds and their practical utility in selective metal ion detection. The dual click reactions were smoothly proceeded under microwave irradiation between silylated 3,4-di-O-propynyl gluco- or galactoside and 3-azidocoumarin, forming fluorescently reactivated bis-triazolocoumarins on sugar templates. Subsequent desilylation resulted in the OH-glycosides with desired water solubility. The following photochemical study disclosed that their fluorescence could be uniquely quenched by silver(I) in aqueous media with very minor responses to the addition of other metal ions. This research would presumably prompt the efficient creation of water soluble and potentially low toxic chemosensors via the fluorogenic dual click chemistry in using the universally existent sugars as the central scaffold. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.03.068
• 作为产物：
  描述：

  t-butyldimethylsilane 、 Α-D-乳酸吡喃糖苷甲酯 在 [Ir(COD)(PPh3)2]SbF6 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 以41%的产率得到methyl 3,6-di-O-(tert-butyldimethylsilyl)-α-D-galactopyranoside
  参考文献：
  名称：

  Regioselectively Trisilylated Hexopyranosides through Homogeneously Catalyzed Silane Alcoholysis

  摘要：

  The iridium complex [Ir(COD)(PPh3)(2)]+SbF6- reacts with tert-butyldimethylsi lane in DMA to form [IrH2(Sol)(2)(PPh3)(2)]+SbFr6-, which is an active catalyst for the regioselective di- and trisilylation of a series of representative methyl h exopyranosides, beta-1,6-anhydrohexopyranosides and 1,3,5-O-methylidene inositol. The corresponding 2,3,6- and 2,4,6-silylated glycosides are obtained in a separable mixture of 47-89% (2,3,6-isomers) and 9-25% (2,4,6-isomers) yield in a single-pot reaction. The 2,4-disilylated derivatives of mannosan, galactosan, and 1,3,5-O-methylidene inositol as well as persilylated levoglucosan are accessible in > 85% yield by this method. The homogeneous nature of the catalysts is a prerequisite for the effective di-/trisilylation, as nanoparticle colloid catalysts generated in situ from Pd-2(dba)(3) (similar to 1.5 nm average particle size) or Ru2Cl5(MeCN)(7) (similar to 0.65 nm average particle size) result in only low yields.

  DOI：

  10.1021/ja056283i

文献信息

• Regioselective Silylation of Sugars through Palladium Nanoparticle-Catalyzed Silane Alcoholysis
  作者：Mee-Kyung Chung、Galina Orlova、John D. Goddard、Marcel Schlaf、Robert Harris、Terrance J. Beveridge、Gisele White、F. Ross Hallett

  DOI：10.1021/ja026723v

  日期：2002.9.1

  silylation of levoglucosan and 1,3,5-O-methylidene-myo-inositol. In an attempt to rationalize the observed regioselectivities, ab initio predictions (HF/3-21G) have been made on the relative energies of some of the silylated products. They suggest that the observed regioselectivities do not reflect a kinetic vs thermodynamic product distribution but are induced by the silylation agent employed. Models

  使用叔丁基二甲基硅烷 (TBDMS-H) 和 Ph(3)SiH 作为硅烷，钯 (0) 催化的硅烷醇解首次应用于糖类。催化剂是 Pd(0) 的胶体溶液，由 PdX(2)（X = Cl(-)、OAc(-)）和 TBDMS-H 在 N,N-二甲基乙酰胺中原位生成。该胶体已通过动态光散射和透射电子显微镜进行表征，并由直径约 2 nm 的催化高活性纳米粒子组成。硅烷醇解反应是甲基和苯基糖苷区域选择性硅烷化的有效方法，并产生氢气作为唯一的副产物。对于许多研究的糖底物，所获得的区域异构体的分布与传统的 R(3)SiCl/碱（碱 = 吡啶，咪唑）方法，并方便地获得 3,6- 而不是 2,6- 甲硅烷基化吡喃糖苷，通过甲硅烷基氯化法获得的主要产品。该方法还允许左旋葡聚糖和 1,3,5-O-亚甲基肌醇的选择性轴向甲硅烷基化。为了使观察到的区域选择性合理化，已经对一些硅烷化产物的相对能量进行了从头预测 (HF/
• Practical method for hydroxyl-group protection using strontium metal and readily available silyl chlorides
  作者：Norikazu Miyoshi、Aki Miyoshi、Yasuaki Miyazaki、Shigeki Kubo、Masaharu Ueno

  DOI：10.1039/d2cc01105k

  日期：——

  We have found that the etherification of silyl-protected secondary alcohols proceeds smoothly in the presence of strontium metal using silyl chloride instead of the expensive, yet more reactive, and commonly used silyl triflate. The reaction occurred almost completely with various alcohols.

  我们发现，甲硅烷基保护的仲醇的醚化在锶金属存在下使用甲硅烷基氯代替昂贵但更活泼且常用的三氟甲磺酸甲硅烷基酯的情况下顺利进行。用各种醇几乎完全发生反应。
• Studies of the selective silylation of methyl α- and β-d-aldohexopyranosides: stability of the partially protected derivatives in polar solvents
  作者：Thérèse Halmos、Roland Montserret、Jean Filippi、Kostas Antonakis

  DOI：10.1016/0008-6215(87)85005-x

  日期：1987.12

  Treatment of methyl .alpha.- (1) and .beta.-D-glucopyranosides, methyl .alpha.- (3) and .beta.-D-galactopyranosides, and methyl .alpha.-D-mannopyranoside (5) with 2, 3, or 4 mol. equiv. of tert-butyldimethylsilyl (TBDMS) chloride under two conditions afforded mixtures of TBDMS ethers which were identified. The following compounds were isolated in synthetically useful yields, the 2,6-di-TBDMS ether of 1 (70%), the 2,6-di- and 2,3,6-tri-TBDMS ethers of 3 (84% and 57%, respectively), and the 2,6-di- and 3,6-di-TBDMS ethers of 5 (50% and 80%, respectively). In dipolar solvents, no migration of the TBDMS groups was detected between partially silylated hydroxyl groups, but the addition of a base (triethylamine or imidazole) caused migration to vicinal cis positions.
• Regioselectively Trisilylated Hexopyranosides through Homogeneously Catalyzed Silane Alcoholysis
  作者：Mee-Kyung Chung、Marcel Schlaf

  DOI：10.1021/ja056283i

  日期：2005.12.1

  The iridium complex [Ir(COD)(PPh3)(2)]+SbF6- reacts with tert-butyldimethylsi lane in DMA to form [IrH2(Sol)(2)(PPh3)(2)]+SbFr6-, which is an active catalyst for the regioselective di- and trisilylation of a series of representative methyl h exopyranosides, beta-1,6-anhydrohexopyranosides and 1,3,5-O-methylidene inositol. The corresponding 2,3,6- and 2,4,6-silylated glycosides are obtained in a separable mixture of 47-89% (2,3,6-isomers) and 9-25% (2,4,6-isomers) yield in a single-pot reaction. The 2,4-disilylated derivatives of mannosan, galactosan, and 1,3,5-O-methylidene inositol as well as persilylated levoglucosan are accessible in > 85% yield by this method. The homogeneous nature of the catalysts is a prerequisite for the effective di-/trisilylation, as nanoparticle colloid catalysts generated in situ from Pd-2(dba)(3) (similar to 1.5 nm average particle size) or Ru2Cl5(MeCN)(7) (similar to 0.65 nm average particle size) result in only low yields.
• Creation of 3,4-bis-triazolocoumarin–sugar conjugates via flourogenic dual click chemistry and their quenching specificity with silver(I) in aqueous media
  作者：Xiao-Peng He、Zhuo Song、Zhi-Zhou Wang、Xiao-Xin Shi、Kaixian Chen、Guo-Rong Chen

  DOI：10.1016/j.tet.2011.03.068

  日期：2011.5

  Fluorogenic click chemistry has recently emerged as an ingenious and powerful tool toward numerous biochemical purposes. We describe herein the use of dual click chemistry toward the fluorescence restoration of a fluorogenic coumarin on epimeric dipropargyl sugar scaffolds and their practical utility in selective metal ion detection. The dual click reactions were smoothly proceeded under microwave irradiation between silylated 3,4-di-O-propynyl gluco- or galactoside and 3-azidocoumarin, forming fluorescently reactivated bis-triazolocoumarins on sugar templates. Subsequent desilylation resulted in the OH-glycosides with desired water solubility. The following photochemical study disclosed that their fluorescence could be uniquely quenched by silver(I) in aqueous media with very minor responses to the addition of other metal ions. This research would presumably prompt the efficient creation of water soluble and potentially low toxic chemosensors via the fluorogenic dual click chemistry in using the universally existent sugars as the central scaffold. (C) 2011 Elsevier Ltd. All rights reserved.