ethyl 3-O-benzyl-6-O-tert-butyldimethylsilyl-1-O-(4,4'-dimethoxytriphenyl)methyl-2-thio-β-D-fructofuranoside | 302905-20-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: ethyl 3-O-benzyl-6-O-tert-butyldimethylsilyl-1-O-(4,4'-dimethoxytriphenyl)methyl-2-thio-β-D-fructofuranoside
• 英文别名: DMT(-1)[Bn(-3)][TBDMS(-6)]Fruf(b)-SEt；(2R,3R,4S,5S)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-ethylsulfanyl-4-phenylmethoxyoxolan-3-ol
• CAS: 302905-20-0
• 化学式: C₄₂H₅₄O₇SSi
• 分子量: 731.038
• InChiKey: HXUAQEXFEHZOIM-KSSIXINKSA-N

物化性质

• 沸点：
  758.2±60.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.83
• 重原子数：
  51
• 可旋转键数：
  17
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  ethyl 3-O-benzyl-6-O-tert-butyldimethylsilyl-1-O-(4,4'-dimethoxytriphenyl)methyl-2-thio-β-D-fructofuranoside 在 palladium on activated charcoal 咪唑 、 三乙基硅烷 、 Amberlite IR-45(OH-) 、 di-tert-butylmethylpyridine 、 氢气 、 DMTST 、 tris(dimethylamino)sulfonium trimethylsilyldifluoride 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 氯仿 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， -35.0~20.0 ℃ 、758.44 kPa 条件下， 反应 8.0h， 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：

  4,4'-双甲氧基三苯甲基氯 在 吡啶 、 4-二甲氨基吡啶 、 sodium hydroxide 、 四丁基硫酸氢铵 作用下， 以 二氯甲烷 为溶剂， 反应 124.0h， 生成 ethyl 3-O-benzyl-6-O-tert-butyldimethylsilyl-1-O-(4,4'-dimethoxytriphenyl)methyl-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

• Hydrogen-Bond-Mediated Aglycone Delivery: Synthesis of β-<scp>d</scp>-Fructofuranosides
  作者：Pan Wang、Yidian Mo、Xiaoyu Cui、Xuyang Ding、Xiao Zhang、Zhongjun Li

  DOI：10.1021/acs.orglett.0c00702

  日期：2020.4.17

  work, we developed an efficient method for the synthesis of β-d-fructofuranosides by using a 6-picoloyl-protected fructofuranosyl thioglycoside as the glycosyl donor. Subsequently, we applied the approach to a wide variety of donors and acceptors. Furthermore, the successful synthesis of levantetrose confirmed its applicability in the multistep synthesis of oligosaccharides.

  β- d-果糖呋喃糖苷键的构建是碳水化合物化学中的主要挑战之一。在这项工作中，我们开发了用于β-的合成的有效方法d通过使用6 picoloyl保护的果糖基硫代糖苷作为糖基供体-fructofuranosides。随后，我们将该方法应用于各种捐赠者和接受者。此外，Levantetrose的成功合成证实了其在寡糖的多步合成中的适用性。
• Chemical Syntheses of Inulin and Levan Structures
  作者：Stefan Oscarson、Fernando W. Sehgelmeble

  DOI：10.1021/jo020341q

  日期：2002.11.1

  beta-D-fructofuranoside 6-OH and 1-OH acceptors (3 and 6) gave stereospecifically the protected methyl levanobioside 12 and inulinobioside 17 in excellent yields (80 and 86%), respectively. Protecting group manipulations on these afforded new disaccharide 6'-OH and 1'-OH acceptors (13 and 19), which were coupled again with donor 11 (1.0 mol equiv) to yield methyl levanotrioside 14 and inulinotrioside 20 in

  果糖呋喃糖基硫糖苷供体，乙基6-O-乙酰基-3-O-苄基-1,4-O-（1,1,3,3-四异丙基二硅氧烷-1,3-二基）-2-硫代-β-D-制备了呋喃呋喃糖苷（11），其设计用于产生立体特异性的β-键并还允许其在6-位和/或1-位上的延长，并用于合成levan和菊粉结构。DMTST促进的11（1.3 mol当量）与甲基β-D-果糖呋喃糖苷6-OH和1-OH受体（3和6）之间的糖基化以优异的产率立体保护了受保护的甲基乙酰左糖苷12和inulinobioside 17（80％和86％） ， 分别。这些上的保护基操作提供了新的二糖6'-OH和1'-OH受体（13和19），将它们与供体11（1.0摩尔当量）再次偶联，以高收率得到了甲基左瓦那糖苷14和inulinotrioside 20、65和67％分别。这些被转化为新的受体，并且也被完全脱保护以提供左旋三糖和次戊三糖的甲基糖苷，所有这些结构先前都无法通过化学合成获得。
• 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.