phenyl 3,4-O-[(2S,3S)-2,3-dimethoxybutan-2,3-yl]-1-thio-β-D-glucopyranoside | 795305-86-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 3,4-O-[(2S,3S)-2,3-dimethoxybutan-2,3-yl]-1-thio-β-D-glucopyranoside
• 英文别名: phenyl 3,4-di-O-(2,3-dimethoxybutane-2,3-diyl)-1-thio-β-D-glucopyranoside；(2S,3S,4aR,5R,7S,8R,8aR)-5-(hydroxymethyl)-2,3-dimethoxy-2,3-dimethyl-7-phenylsulfanyl-5,7,8,8a-tetrahydro-4aH-pyrano[3,4-b][1,4]dioxin-8-ol
• CAS: 795305-86-1
• 化学式: C₁₈H₂₆O₇S
• 分子量: 386.466
• InChiKey: LKDBGATZWLGSIW-MVEAFLSBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  112
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  phenyl 3,4-O-[(2S,3S)-2,3-dimethoxybutan-2,3-yl]-1-thio-β-D-glucopyranoside 在 sodium hydride 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.17h， 生成 phenyl 2,6-di-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a trans-Fused 2,3-O-Carbonate Group

  摘要：

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.

  DOI：

  10.1021/jo0508999
• 作为产物：
  描述：

  1-硫代-b-D-吡喃葡萄糖苷对甲苯酯 、 2,2,3,3-四甲氧基丁烷 在 D(+)-10-樟脑磺酸 、 原甲酸三甲酯 作用下， 以 甲醇 为溶剂， 反应 18.0h， 以39%的产率得到phenyl 2,3-di-O-(2,3-dimethoxybutane-2,3-diyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  通过亲核取代合成 6-磺基甲基硫糖苷：防止硫糖苷 6-O-三氟甲磺酸酯 1→6 异头基团迁移的方法

  摘要：

  描述了通过相应 6-O-三氟甲磺酸酯的亲核置换将磺基甲基部分引入硫糖苷的主要位置。通过使用 α-硫糖苷或构象锁定的 β-硫糖苷作为起始材料，可以防止异头基团从构象灵活的 β-硫糖苷中不可避免地通过双环锍离子中间体发生 1→6 迁移。硫糖苷 6-磺酸在合成含肝素三糖的糖醛酸过程中表现出优异的 α 选择性。

  DOI：

  10.1002/ejoc.201300681

文献信息

• Ready Transformation of Partially Unprotected Thioglycosides into Glycosyl Fluorides Mediated by NIS/HF-Pyridine or Et₃N·3HF
  作者：J. Cristóbal López、Paloma Bernal-Albert、Clara Uriel、Ana M. Gómez

  DOI：10.1002/ejoc.200800754

  日期：2008.10

  The transformation of partially unprotected phenyl 1-thioglycosides into glycosyl fluorides can be conveniently carried out by treatment with NIS in the presence of HF–pyridine. Other sources of halonium ions such as NBS, IDCP, have also been employed. The combination NIS/Et3N·3HF, where triethylamine–tris(hydrogen fluoride) (Et3N·3HF) replaces HF–pyridine, can also effect this transformation when

  在 HF-吡啶存在下用 NIS 处理可以方便地将部分未保护的苯基 1-硫代糖苷转化为糖基氟。还使用了其他卤离子源，例如 NBS、IDCP。当存在对酸敏感的取代基时，NIS/Et3N·3HF 组合（其中三乙胺-三（氟化氢）（Et3N·3HF）代替 HF-吡啶）也可以影响这种转化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Synthesis of Potassium (2R)-2-O-α-D-Mannopyranosyl-(1→2)-α-D-glucopyranosyl-2,3-dihydroxypropanoate: A Naturally Compatible Solute
  作者：Eva C. Lourenço、M. Rita Ventura

  DOI：10.1002/ejoc.201100934

  日期：2011.11

  An expedient synthesis of the potassium salt of (2R)-2-O-α-D-mannopyranosyl-(12)-α-D-glucopyranosyl-2,3-dihydroxypropanoic acid (MGG)―a recently isolated, rare, compatible solute―was accomplished. A bis-acetal-protected thioglucoside, 6-OTBDPS, with a 2-OH group was used as the acceptor in the first glycosylation reaction with tetraacetylmannosyl trichloroacetimidate, and as the donor in the glycosylation

  (2R)-2-O-α-D-吡喃甘露糖基-(12)-α-D-吡喃葡萄糖基-2,3-二羟基丙酸 (MGG) 钾盐的便利合成——一种最近分离的、稀有的、相容的溶质——大功告成。带有 2-OH 基团的双缩醛保护的硫葡糖苷 6-OTBDPS 在与四乙酰甘露糖基三氯乙酰亚胺酯的第一次糖基化反应中用作受体，并在与甘油酸酯衍生物的糖基化反应中用作供体。α-端基异构体是两种糖基化反应的唯一产物，正如预期形成 α-甘露糖苷。1,2-顺式葡萄糖苷的形成更具挑战性。
• Design and Synthesis of 5‘-Deoxy-5‘-Phenyladenophostin A, a Highly Potent IP₃ Receptor Ligand¹
  作者：Tetsuya Mochizuki、Yoshihiko Kondo、Hiroshi Abe、Colin W. Taylor、Barry V. L. Potter、Akira Matsuda、Satoshi Shuto

  DOI：10.1021/ol0602710

  日期：2006.3.1

  5'-Deoxy-5'-phenyladenophostin A (5), designed as a useful IP3 receptor ligand based on the previous structure-activity relationship studies, was successfully synthesized via two key stereoselective glycosidation steps. This compound proved to be a highly potent IP3 receptor agonist.
• Synthesis of 6-Sulfonatomethyl Thioglycosides by Nucleophilic Substitution: Methods to Prevent 1→6 Anomeric Group Migration of Thioglycoside 6-<i>O</i>-Triflates
  作者：Mihály Herczeg、Erika Mező、Dániel Eszenyi、László Lázár、Magdolna Csávás、Ilona Bereczki、Sándor Antus、Anikó Borbás

  DOI：10.1002/ejoc.201300681

  日期：2013.9

  position of thioglycosides by nucleophilic displacement of the corresponding 6-O-triflate is described. The 1→6 migration of the anomeric group, which inevitably occurs through a bicyclic sulfonium ion intermediate, from conformationally flexible β-thioglycosides was prevented by using an α-thioglycoside or conformationally locked β-thioglycoside as the starting material. The thioglycoside 6-sulfonic

  描述了通过相应 6-O-三氟甲磺酸酯的亲核置换将磺基甲基部分引入硫糖苷的主要位置。通过使用 α-硫糖苷或构象锁定的 β-硫糖苷作为起始材料，可以防止异头基团从构象灵活的 β-硫糖苷中不可避免地通过双环锍离子中间体发生 1→6 迁移。硫糖苷 6-磺酸在合成含肝素三糖的糖醛酸过程中表现出优异的 α 选择性。
• Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a <i>trans</i>-Fused 2,3-<i>O</i>-Carbonate Group
  作者：David Crich、Prasanna Jayalath

  DOI：10.1021/jo0508999

  日期：2005.9.1

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.