methyl 3,4,6-tris(t-butyldimethylsilyl)-α-D-mannopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,4,6-tris(t-butyldimethylsilyl)-α-D-mannopyranoside
• 英文别名: methyl 3,4,6-tri-O-TBDMS-α-D-mannopyranoside；TBDMS(-3)[TBDMS(-4)][TBDMS(-6)]a-Man1Me；(2S,3S,4R,5R,6R)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-methoxyoxan-3-ol
• 化学式: C₂₅H₅₆O₆Si₃
• 分子量: 536.973
• InChiKey: JQGFZTJXWOXMLN-YHINDDMVSA-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：

  methyl 3,4,6-tris-O-(tert-butyldimethylsilyl)-2-deoxy-2-iodo-α-D-mannopyranoside 在 air 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 甲苯 为溶剂， 反应 3.0h， 生成 methyl 3,4,6-tris(t-butyldimethylsilyl)-α-D-mannopyranoside 、
  参考文献：
  名称：

  用分子氧自由基氧化2-脱氧-2-碘六吡喃果糖苷

  摘要：

  2-脱氧-2-碘六吡喃糖苷与分子氧和三丁基锡烷反应，以高收率和适度的选择性产生差向异构的C-2醇。

  DOI：

  10.1016/0040-4039(94)88272-x

文献信息

• Tandem Epoxidation‐Alcoholysis or Epoxidation‐Hydrolysis of Glycals Catalyzed by Titanium(IV) Isopropoxide or Venturello’s Phosphotungstate Complex
  作者：Pieter Levecque、David W. Gammon、Henok Hadgu Kinfe、Pierre Jacobs、Dirk De Vos、Bert Sels

  DOI：10.1002/adsc.200800079

  日期：2008.7.7

  Venturello’s phosphotungstate complex and titanium(IV) isopropoxide [Ti(O-i-Pr)4] were successfully used as catalysts for the epoxidation-alcoholysis of glycals using hydrogen peroxide [H2O2]. Reaction substrates included a range of variously protected glycals and different alcohols were used as solvents. Ti(O-i-Pr)4 was only effective in methanol as solvent, but gave methyl glycosides in high yields

  Venturello的磷钨酸盐络合物和异丙醇钛（IV）[Ti（O- i- Pr）4 ]已成功用作使用过氧化氢[H 2 O 2 ]的环氧乙烷缩合醇解的催化剂。反应底物包括各种受保护的糖基，不同的醇用作溶剂。钛（O- i- Pr）4仅在甲醇作为溶剂中有效，但以高收率和高选择性得到甲基糖苷。事实证明，Ventrollo复合物是一种用途广泛且高效的催化剂。除了在醇类溶剂中进行环氧化-醇解以外，它还显示了在双相条件下的活性，以允许长链醇的糖基化，并且在苄基化的葡糖的立体选择性二羟基化中非常有效。
• 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.