methyl 2,3,6-tri-O-tert-butyldimethylsilyl-β-D-glucopyranoside | 116144-14-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,6-tri-O-tert-butyldimethylsilyl-β-D-glucopyranoside
• 英文别名: methyl 2,3,6-tris(t-butyldimethylsilyl)-β-D-glucopyranoside；TBDMS(-2)[TBDMS(-3)][TBDMS(-6)]b-Glc1Me；(2R,3R,4S,5R,6R)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-methoxyoxan-3-ol
• CAS: 116144-14-0
• 化学式: C₂₅H₅₆O₆Si₃
• 分子量: 536.973
• InChiKey: CHJIUQMYTRPUCJ-QMCAAQAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.52
• 重原子数：
  34
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  甲基 Β-D-吡喃葡萄糖苷 在 [Ir(COD)(PPh3)2]SbF6 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 生成 methyl 2,3,6-tri-O-tert-butyldimethylsilyl-β-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

• 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.