2,6-O-bis(tert-butyldimethylsilanyl)-1-O-methyl-β-D-galactopyranoside | 74247-71-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,6-O-bis(tert-butyldimethylsilanyl)-1-O-methyl-β-D-galactopyranoside
• 英文别名: methyl 2,6-di-O-(tert-butyldimethylsilyl)-β-D-galactopyranoside；methyl 2,6-di-O-tert-butyldimethylsilyl-β-D-galactopyranoside；Methyl-2,6-bis-O-(t-butyldimethylsilyl)-β-D-galaktopyranosid；TBDMS(-2)[TBDMS(-6)]b-Gal1Me；(2R,3R,4S,5R,6R)-5-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-methoxyoxane-3,4-diol
• CAS: 74247-71-5
• 化学式: C₁₉H₄₂O₆Si₂
• 分子量: 422.71
• InChiKey: IYOLDHREOIQTQU-DRRXZNNHSA-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：

  2,6-O-bis(tert-butyldimethylsilanyl)-1-O-methyl-β-D-galactopyranoside 在 正丁基锂 、 草酰氯 、 四丁基氟化铵 、 二甲基亚砜 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 159.0h， 生成 methyl 6,7-dideoxy-3,4-di-O-(methoxymethyl)-2-O-(tert-butyldimethylsilyl)-β-D-galacto-hept-6-enopyranoside
  参考文献：
  名称：

  Direct carbohydrate to carbocycle conversions via intramolecular allylation with Et2Zn/Pd(0)

  摘要：

  Treatment of 5-vinylpyranosides with Et2Zn and catalytic Pd(0), in the presence of ZnCl2, results in the formation of 5-membered carbocyclic products. This carbohydrate ring-contraction features an intramolecular allylation of a ring-opened carbohydrate aldehyde by an in situ-generated nucleophilic allylzinc species. The stereoselectivity about vinyl and free hydroxyl groups at the newly created stereogenic centers varies from low to moderate while both its extent and sense are found to depend on particular structural features (e.g. the configuration of the starting carbohydrate). (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00825-1
• 作为产物：
  描述：

  甲基-Β-D-吡喃半乳糖苷 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 甲酸 、 硫酸 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 48.2h， 生成 2,6-O-bis(tert-butyldimethylsilanyl)-1-O-methyl-β-D-galactopyranoside
  参考文献：
  名称：

  Direct carbohydrate to carbocycle conversions via intramolecular allylation with Et2Zn/Pd(0)

  摘要：

  Treatment of 5-vinylpyranosides with Et2Zn and catalytic Pd(0), in the presence of ZnCl2, results in the formation of 5-membered carbocyclic products. This carbohydrate ring-contraction features an intramolecular allylation of a ring-opened carbohydrate aldehyde by an in situ-generated nucleophilic allylzinc species. The stereoselectivity about vinyl and free hydroxyl groups at the newly created stereogenic centers varies from low to moderate while both its extent and sense are found to depend on particular structural features (e.g. the configuration of the starting carbohydrate). (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00825-1

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.
• Strukturelle Abwandlungen an partiell silylierten Kohlenhydraten mittels Triphenylphosphan/Azodicarbons�urediethylester, 4. Mitt.: Transformationen an Mannose und Galaktose
  作者：Edgar Mark、Erich Zbiral、Hannelore H. Brandstetter

  DOI：10.1007/bf00938735

  日期：——
• Direct carbohydrate to carbocycle conversions via intramolecular allylation with Et2Zn/Pd(0)
  作者：José M Aurrecoechea、Mónica Arrate、Jesús H Gil、Beatriz López

  DOI：10.1016/s0040-4020(03)00825-1

  日期：2003.7

  Treatment of 5-vinylpyranosides with Et2Zn and catalytic Pd(0), in the presence of ZnCl2, results in the formation of 5-membered carbocyclic products. This carbohydrate ring-contraction features an intramolecular allylation of a ring-opened carbohydrate aldehyde by an in situ-generated nucleophilic allylzinc species. The stereoselectivity about vinyl and free hydroxyl groups at the newly created stereogenic centers varies from low to moderate while both its extent and sense are found to depend on particular structural features (e.g. the configuration of the starting carbohydrate). (C) 2003 Elsevier Science Ltd. All rights reserved.