methyl 3,6-di-O-tert-butyldimethylsilyl-α-D-glucopyranoside | 68102-62-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,6-di-O-tert-butyldimethylsilyl-α-D-glucopyranoside
• 英文别名: 3,6-O-bis(tert-butyldimethylsilanyl)-1-O-methyl-α-D-glucopyranoside；TBDMS(-3)[TBDMS(-6)]a-Glc1Me；(2R,3R,4S,5R,6S)-4-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-methoxyoxane-3,5-diol
• CAS: 68102-62-5
• 化学式: C₁₉H₄₂O₆Si₂
• 分子量: 422.71
• InChiKey: XKWIWIFQWYUHBQ-MTSZKFMLSA-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：

  乙酰溴 、 methyl 3,6-di-O-tert-butyldimethylsilyl-α-D-glucopyranoside 在 tin(II) bromide 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以86%的产率得到2,3,4,6-四-o-乙酰基-alpha-d-吡喃葡萄糖苷甲酯
  参考文献：
  名称：

  A one-step and chemoselective conversion of silyl-protected alcohols into the corresponding acetates

  摘要：

  A reagent system of acetyl bromide combined with a catalytic amount of tin(II) bromide cleaves readily trialkylsilyl ethers to give the corresponding acetates in high yields under very mild conditions.

  DOI：

  10.1016/s0040-4039(00)73040-1
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 alpha-甲基葡萄糖甙 在 吡啶 、 四丁基溴化铵 作用下， 反应 4.5h， 以60%的产率得到methyl 3,6-di-O-tert-butyldimethylsilyl-α-D-glucopyranoside
  参考文献：
  名称：

  通过基于区域选择性甲硅烷基化的无溶剂一锅序列对糖类多元醇进行正交保护。

  摘要：

  鉴于叔丁基二甲基甲硅烷基（TBDMS）和叔丁基二苯基甲硅烷基（TBDPS）与各种条件的相容性，它们是在有机合成中广泛使用的醇保护基。它们在多元醇上的区域选择性安装通常需要漫长的反应和使用高沸点溶剂。在本文的第一部分中，我们证明了糖多元醇的区域选择性甲硅烷基化可以在短时间内使用必需的甲硅烷基氯和非常有限的过量吡啶（2-3当量）进行。在这些条件下，考虑到多元醇底物的不溶性，可以认为是无溶剂条件，该反应比文献中报道的大多数实例都更快，甚至可以用催化量的四丁基溴化铵（ TBAB）。事实证明，该策略对于选择性保护TBDMS仲醇或糖多元醇的快速全O-三甲基甲硅烷基化也很有用。在本文的第二部分中，随着前所未有的“一锅”和“无溶剂”序列的发展，硅烷化方法的范围得到了显着扩展，从而允许糖多元醇的区域选择性甲硅烷基化/烷基化（或反向序列）时代。所开发的方法代表了一种非常有用且实验简单的工具，可直接获取可用于有

  DOI：

  10.3762/bjoc.12.271

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/
• 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.
• 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.
• A one-step and chemoselective conversion of silyl-protected alcohols into the corresponding acetates
  作者：Takeshi Oriyama、Mihoko Oda、Junko Gono、Gen Koga

  DOI：10.1016/s0040-4039(00)73040-1

  日期：1994.3

  A reagent system of acetyl bromide combined with a catalytic amount of tin(II) bromide cleaves readily trialkylsilyl ethers to give the corresponding acetates in high yields under very mild conditions.
• Orthogonal protection of saccharide polyols through solvent-free one-pot sequences based on regioselective silylations
  作者：Serena Traboni、Emiliano Bedini、Alfonso Iadonisi

  DOI：10.3762/bjoc.12.271

  日期：——

  either the selective TBDMS protection of secondary alcohols or the fast per-O-trimethylsilylation of saccharide polyols. In the second part of the paper the scope of the silylation approach was significantly extended with the development of unprecedented "one-pot" and "solvent-free" sequences allowing the regioselective silylation/alkylation (or the reverse sequence) of saccharide polyols in short times

  鉴于叔丁基二甲基甲硅烷基（TBDMS）和叔丁基二苯基甲硅烷基（TBDPS）与各种条件的相容性，它们是在有机合成中广泛使用的醇保护基。它们在多元醇上的区域选择性安装通常需要漫长的反应和使用高沸点溶剂。在本文的第一部分中，我们证明了糖多元醇的区域选择性甲硅烷基化可以在短时间内使用必需的甲硅烷基氯和非常有限的过量吡啶（2-3当量）进行。在这些条件下，考虑到多元醇底物的不溶性，可以认为是无溶剂条件，该反应比文献中报道的大多数实例都更快，甚至可以用催化量的四丁基溴化铵（ TBAB）。事实证明，该策略对于选择性保护TBDMS仲醇或糖多元醇的快速全O-三甲基甲硅烷基化也很有用。在本文的第二部分中，随着前所未有的“一锅”和“无溶剂”序列的发展，硅烷化方法的范围得到了显着扩展，从而允许糖多元醇的区域选择性甲硅烷基化/烷基化（或反向序列）时代。所开发的方法代表了一种非常有用且实验简单的工具，可直接获取可用于有