methyl 2,3,4,6-tetrakis-O-(tert-butyldimethylsilyl)-α-D-mannopyranoside | 116144-33-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4,6-tetrakis-O-(tert-butyldimethylsilyl)-α-D-mannopyranoside
• 英文别名: methyl 2,3,4,6-tetra-O-tert-butyldimethylsilyl-α-D-mannopyranoside；TBDMS(-2)[TBDMS(-3)][TBDMS(-4)][TBDMS(-6)]a-Man1Me；[(2R,3R,4S,5S,6S)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-methoxyoxan-4-yl]oxy-tert-butyl-dimethylsilane
• CAS: 116144-33-3
• 化学式: C₃₁H₇₀O₆Si₄
• 分子量: 651.235
• InChiKey: CLDPSINVZRPNOV-VKINHPFQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.55
• 重原子数：
  41
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4,6-tetrakis-O-(tert-butyldimethylsilyl)-α-D-mannopyranoside 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 19.0h， 生成 甲基-D-丙噻
  参考文献：
  名称：

  Operationally Simple and Efficient Workup Procedure for TBAF-Mediated Desilylation:  Application to Halichondrin Synthesis

  摘要：

  An operationally simple and efficient workup method for tetrabutylammonium fluoride (TBAF)-mediated t-butyldimethylsilyl (TBS) deprotection has been developed. The procedure includes addition of a sulfonic acid resin and calcium carbonate, followed by filtration and evaporation. This method eliminates the tedious aqueous-phase extraction process to remove excess TBAF and materials derived from TBAF, thereby making the protocol highly amenable to multiple TBS deprotections. Its efficiency and usefulness were demonstrated by using the transformation of 1a to 3a in the halichondrin synthesis.

  DOI：

  10.1021/ol063113h
• 作为产物：
  描述：

  甲基-D-丙噻 在 [Ir(COD)(PPh3)2]SbF6 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 生成 methyl 2,3,4,6-tetrakis-O-(tert-butyldimethylsilyl)-α-D-mannopyranoside
  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.