ethyl 3-O-benzyl-6-O-tert-butyldimethylsilyl-1,4-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2-thio-β-D-fructofuranoside | 302905-22-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl 3-O-benzyl-6-O-tert-butyldimethylsilyl-1,4-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2-thio-β-D-fructofuranoside
• 英文别名: tert-butyl-[[(1R,8S,10R,11S)-8-ethylsulfanyl-11-phenylmethoxy-3,3,5,5-tetra(propan-2-yl)-2,4,6,9-tetraoxa-3,5-disilabicyclo[6.2.1]undecan-10-yl]methoxy]-dimethylsilane
• CAS: 302905-22-2
• 化学式: C₃₃H₆₂O₆SSi₃
• 分子量: 671.174
• InChiKey: LIIJIVWDBLIHOG-QFBUMDDISA-N

物化性质

• 沸点：
  587.5±50.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.4
• 重原子数：
  43
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  80.7
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl 3-O-benzyl-6-O-tert-butyldimethylsilyl-1,4-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2-thio-β-D-fructofuranoside 在 palladium on activated charcoal Amberlite IR-45(OH-) 、 di-tert-butylmethylpyridine 、 氢气 、 DMTST 、 tris(dimethylamino)sulfonium trimethylsilyldifluoride 作用下， 以 甲醇 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 20.0 ℃ 、758.44 kPa 条件下， 反应 3.0h， 生成 蔗糖
  参考文献：
  名称：

  A Novel β-Directing Fructofuranosyl Donor Concept. Stereospecific Synthesis of Sucrose

  摘要：

  A new concept for the construction of beta-D-fructofuranosides based on the idea of locking the anomeric CH2OH group to the alpha-side through an internal bridge to the 4-hydroxyl group is presented. Thioglycoside fructose donors containing an internal 1,4-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl) (TIPS) acetal bridge have been constructed and used in glycosylations with dimethyl(thiomethyl)sulfonium triflate (DMTST) as promoter. The couplings were stereospecific to give beta-D-fructofuranosyl disaccharides in high yields. Using this approach, sucrose has been synthesized stereospecifically in 80% yield.

  DOI：

  10.1021/ja001439u
• 作为产物：
  描述：

  ethyl 2-thio-β-D-fructofuranoside 在 吡啶 、 咪唑 、 三乙基硅烷 、 4-二甲氨基吡啶 、 sodium hydroxide 、 四丁基硫酸氢铵 、 三氟乙酸 作用下， 以 二氯甲烷 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 129.0h， 生成 ethyl 3-O-benzyl-6-O-tert-butyldimethylsilyl-1,4-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2-thio-β-D-fructofuranoside
  参考文献：
  名称：

  A Novel β-Directing Fructofuranosyl Donor Concept. Stereospecific Synthesis of Sucrose

  摘要：

  A new concept for the construction of beta-D-fructofuranosides based on the idea of locking the anomeric CH2OH group to the alpha-side through an internal bridge to the 4-hydroxyl group is presented. Thioglycoside fructose donors containing an internal 1,4-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl) (TIPS) acetal bridge have been constructed and used in glycosylations with dimethyl(thiomethyl)sulfonium triflate (DMTST) as promoter. The couplings were stereospecific to give beta-D-fructofuranosyl disaccharides in high yields. Using this approach, sucrose has been synthesized stereospecifically in 80% yield.

  DOI：

  10.1021/ja001439u

文献信息

• A stereoselective approach to phosphodiester-linked oligomers of the repeating unit of Escherichia coli K52 capsular polysaccharide containing β-D-fructofuranosyl moieties
  作者：Stefan Oscarson、Fernando W. Sehgelmeble

  DOI：10.1016/j.tetasy.2004.11.051

  日期：2005.1

  A stereoselective synthesis of a dimer, β-D-Fruf-(2→2)-α-D-Galp-(1-PO3H-3)-[β-D-Fruf-(2→2)]-D-Galp, of the repeating unit of the K52 type CPS of E. coli is described. The β-fructofuranosyl residue was introduced in a DMTST-promoted coupling using a 1,4-TIPS-bridged thiofructofuranoside donor and a 2-OH TMSE galactoside acceptor affording exclusively the β-linked disaccharide. Protecting group manipulation

  二聚体，β-d-的Fru的立体选择性合成˚F - （2→2）-α-d-Gal的p - （1-PO 3 H-3） - [β-d-的Fru ˚F - （2→2） ] -D-Gal p，是大肠杆菌K52型CPS的重复单元描述。使用1，4-TIPS桥连的硫代果糖呋喃糖苷供体和2-OH TMSE半乳糖苷受体将D-果糖呋喃糖基残基引入DMTST促进的偶联中，仅提供β-连接的二糖。该二糖的保护基操纵产生了3-OH受体和还原二糖，它们使用H-膦酸酯化学经由磷酸二酯桥连接。半缩醛仅以α-端基异构体形式存在，为什么膦酰化可以立体选择性地产生α-H-膦酸酯单酯。在3-OH二糖受体存在下用新戊酰氯活化后者，然后进行I 2-氧化，以高收率得到目标二聚体。
• A Novel β-Directing Fructofuranosyl Donor Concept. Stereospecific Synthesis of Sucrose
  作者：Stefan Oscarson、Fernando W. Sehgelmeble

  DOI：10.1021/ja001439u

  日期：2000.9.1

  A new concept for the construction of beta-D-fructofuranosides based on the idea of locking the anomeric CH2OH group to the alpha-side through an internal bridge to the 4-hydroxyl group is presented. Thioglycoside fructose donors containing an internal 1,4-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl) (TIPS) acetal bridge have been constructed and used in glycosylations with dimethyl(thiomethyl)sulfonium triflate (DMTST) as promoter. The couplings were stereospecific to give beta-D-fructofuranosyl disaccharides in high yields. Using this approach, sucrose has been synthesized stereospecifically in 80% yield.