1,4,6-tri-O-benzyl-2,3-O-[1-(benzyloxy)benzylidene]-β-D-fructofuranose | 178491-57-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: 1,4,6-tri-O-benzyl-2,3-O-[1-(benzyloxy)benzylidene]-β-D-fructofuranose
• CAS: 178491-57-1
• 化学式: C₄₁H₄₀O₇
• 分子量: 644.764
• InChiKey: DINZAKHGHKCHAI-HJRBIJKLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.54
• 重原子数：
  48.0
• 可旋转键数：
  15.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  64.61
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  1,4,6-tri-O-benzyl-2,3-O-[1-(benzyloxy)benzylidene]-β-D-fructofuranose 在 calcium sulfate 、 三氟甲磺酸三甲基硅酯 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 10.58h， 生成 ethyl 1,4,6-tri-O-benzyl-2-thio-β-D-fructofuranoside
  参考文献：
  名称：

  Stereospecific Synthesis of β-d-Fructofuranosides Using Thioglycoside Donors and Internal Aglycon Delivery

  摘要：

  Stereospecific synthesis of beta-D-fructofuranosides has been accomplished by the application of an internal acceptor delivery approach. The acceptor, ethanol or monosaccharides, is initially tethered to the fructofuranose 3-hydroxyl group, adjacent to the anomeric center and on the beta-side of the furanose ring, as part of a mixed p-methoxybenzaldehyde acetal, which is formed by DDQ-oxidation of ethyl 1,4,6-tri-O-benzyl-3-O-(4-methoxybenzyl)-2-thio-D-fructofuranoside in the presence of the acceptor or of the p-methoxybenzylated acceptor in the presence of the corresponding 3-OH fructofuranoside. Then, activation of the thioglycoside with a thiophilic promoter allows the delivery of the acceptor from the acetal to the activated anomeric center to yield the beta-linked fructofuranoside in high yields (76-85%). If promoters with nonnucleophilic anions (triflate, perchlorate) are used, the intermediate acetal decomposes to produce the beta-fructofuranoside products as 3-OH derivatives. However, if NIS is used as promoter, the N-succinimide anion interacts with the benzylidene carbon to give the beta-fructofuranoside products as mixed fructofuranoside-3-O-yl N-succinimide p-methoxybenzaldehyde acetals.

  DOI：

  10.1021/jo970983r
• 作为产物：
  描述：

  1,4,6-tri-O-benzoyl-2,3-O-[1-(benzyloxy)benzylidene]-β-D-fructofuranose 在 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 氯仿 、 N,N-二甲基甲酰胺 、 paraffin 为溶剂， 反应 12.0h， 生成 1,4,6-tri-O-benzyl-2,3-O-[1-(benzyloxy)benzylidene]-β-D-fructofuranose
  参考文献：
  名称：

  Stereospecific Synthesis of β-d-Fructofuranosides Using Thioglycoside Donors and Internal Aglycon Delivery

  摘要：

  Stereospecific synthesis of beta-D-fructofuranosides has been accomplished by the application of an internal acceptor delivery approach. The acceptor, ethanol or monosaccharides, is initially tethered to the fructofuranose 3-hydroxyl group, adjacent to the anomeric center and on the beta-side of the furanose ring, as part of a mixed p-methoxybenzaldehyde acetal, which is formed by DDQ-oxidation of ethyl 1,4,6-tri-O-benzyl-3-O-(4-methoxybenzyl)-2-thio-D-fructofuranoside in the presence of the acceptor or of the p-methoxybenzylated acceptor in the presence of the corresponding 3-OH fructofuranoside. Then, activation of the thioglycoside with a thiophilic promoter allows the delivery of the acceptor from the acetal to the activated anomeric center to yield the beta-linked fructofuranoside in high yields (76-85%). If promoters with nonnucleophilic anions (triflate, perchlorate) are used, the intermediate acetal decomposes to produce the beta-fructofuranoside products as 3-OH derivatives. However, if NIS is used as promoter, the N-succinimide anion interacts with the benzylidene carbon to give the beta-fructofuranoside products as mixed fructofuranoside-3-O-yl N-succinimide p-methoxybenzaldehyde acetals.

  DOI：

  10.1021/jo970983r

文献信息

• 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.
• Stereospecific Synthesis of β-<scp>d</scp>-Fructofuranosides Using the Internal Aglycon Delivery Approach
  作者：Christian Krog-Jensen、Stefan Oscarson

  DOI：10.1021/jo960776b

  日期：1996.1.1