4,6-O-bis(tert-butyldimethylsilanyl)-1-O-methyl-α-D-glucopyranoside

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

  3,4,6-tri-O-benzyl-D-glucal epoxide 、 4,6-O-bis(tert-butyldimethylsilanyl)-1-O-methyl-α-D-glucopyranoside 在 四羟基二硼 作用下， 以 乙腈 为溶剂， 反应 4.0h， 以45%的产率得到
  参考文献：
  名称：

  Diboron催化反式-1,2-二醇的区域和1,2-顺式-α-立体选择性糖基化

  摘要：

  在二硼催化剂存在下，使用1,2-脱水葡萄糖供体和反式-1,2-二醇糖受体研究了区域-和1,2-顺-α-立体选择性糖基化。反应进行顺利，以提供相应的1,2-顺式-α-糖苷，其始终具有非常高的立体选择性，并由受体的保护基团控制了区域选择性。目前的糖基化方法已成功应用于α-1,3-葡聚糖五糖的高效合成。

  DOI：

  10.1021/acs.joc.0c02093
• 作为产物：
  描述：

  t-butyldimethylsilane 、 alpha-甲基葡萄糖甙 在 Ru2(μ-Cl)2Cl2(CO)4(P(CH3)3)2 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 15.0h， 以21%的产率得到2,6-O-bis(tert-butyldimethylsilanyl)-1-O-methyl-α-D-glucopyranoside
  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/
• 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.
• Diboron-Catalyzed Regio- and 1,2-<i>cis</i>-α-Stereoselective Glycosylation of <i>trans</i>-1,2-Diols
  作者：Shunpei Tomita、Masamichi Tanaka、Michitaka Inoue、Kazuki Inaba、Daisuke Takahashi、Kazunobu Toshima

  DOI：10.1021/acs.joc.0c02093

  日期：2020.12.18

  2-cis-α-stereoselective glycosylations were investigated using 1,2-anhydroglucose donors and trans-1,2-diol sugar acceptors in the presence of a diboron catalyst. The reactions proceeded smoothly to provide the corresponding 1,2-cis-α-glycosides with consistently very high stereoselectivity and were regioselectivity controlled by the protecting groups of the acceptor. The present glycosylation method was applied

  在二硼催化剂存在下，使用1,2-脱水葡萄糖供体和反式-1,2-二醇糖受体研究了区域-和1,2-顺-α-立体选择性糖基化。反应进行顺利，以提供相应的1,2-顺式-α-糖苷，其始终具有非常高的立体选择性，并由受体的保护基团控制了区域选择性。目前的糖基化方法已成功应用于α-1,3-葡聚糖五糖的高效合成。