hepta-O-acetyl-1-thio-β-cellobiose | 68636-40-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: hepta-O-acetyl-1-thio-β-cellobiose
• 英文别名: hepta-O-acetyl-1-thio-β-D-cellobiose；2,2',3,3',4',6,6'-hepta-O-acetyl-1-thio-β-D-cellobiose；4-O-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranose；2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranose；(((2R,3R,4S,5R,6S)-4,5-diacetoxy-2-(acetoxymethyl)-6-mercaptotetrahydro-2H-pyran-3-yl)oxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate；2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranose；2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-thio-β-D-glucopyranose；2,3,6,2',3',4',6'-hepta-O-acetyl-1-thio-β-cellobiose；1-thio-β-D-cellobiose O-peracetate；2,3,4,6-tetra-O-acetyl-D-glucopyranosyl-(1->4)-β-D-1-thio-2,3,6-tri-O-acetylglucopyranoside；Glc2Ac3Ac4Ac6Ac(b1-4)b-Glc1SH2Ac3Ac6Ac；[(2R,3R,4S,5R,6S)-3,4,5-triacetyloxy-6-[(2R,3R,4S,5R,6S)-4,5-diacetyloxy-2-(acetyloxymethyl)-6-sulfanyloxan-3-yl]oxyoxan-2-yl]methyl acetate
• CAS: 68636-40-8
• 化学式: C₂₆H₃₆O₁₇S
• 分子量: 652.628
• InChiKey: CBJRSZGMIHOXAN-VRECAULFSA-N

物化性质

• 沸点：
  664.0±55.0 °C(Predicted)
• 密度：
  1.37±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  44
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  213
• 氢给体数：
  1
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  hepta-O-acetyl-1-thio-β-cellobiose 在 碘 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 1.17h， 生成 1,5-diphenylpyrazol-3-yl 2,3,4,6-tetra-O-acetyl-1-thio-β-cellobioside
  参考文献：
  名称：

  Joseph, Benoit; Rollin, Patrick, Journal of Chemical Research, Miniprint, 1994, # 4, p. 770 - 788

  摘要：

  DOI：
• 作为产物：
  描述：

  乙酰溴代纤维二糖 在 L-1,4-二硫代苏糖醇 作用下， 以 N,N-二甲基乙酰胺 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 hepta-O-acetyl-1-thio-β-cellobiose
  参考文献：
  名称：

  受天然化学连接启发的选择性S-脱乙酰化：糖基硫醇和药物巯基类似物的实用合成

  摘要：

  通过在温和的碱性条件下进行简单的硫代酯基转移，即可实现高效的选择性S-脱乙酰基作用。

  DOI：

  10.1039/c5gc00084j

文献信息

• Stereoselective Palladium-Catalyzed Alkenylation and Alkynylation of Thioglycosides
  作者：Etienne Brachet、Jean-Daniel Brion、Mouad Alami、Samir Messaoudi

  DOI：10.1002/adsc.201300419

  日期：2013.9.16

  An efficient and unprecedented palladium‐catalyzed S‐glycosylation reaction of a range of alkenyl and alkynyl halides by using thiosugars as nucleophile partners has been established. With palladium diacetate in combination with Xantphos as the catalytic system, a variety of β‐alkenylthioglycosides as well as β‐alkynylthioglycosides can be prepared in good to excellent yields. The efficiency of this

  通过使用硫糖作为亲核试剂的伙伴，已经建立了有效且前所未有的钯催化的一系列链烯基和炔基卤化物的S-糖基化反应。将二乙酸钯与Xantphos结合用作催化体系，可以制备各种β-烯基硫代糖苷以及β-炔基硫代糖苷，而且收率很高。叶片封闭的β-葡萄糖苷酶抑制剂的正式合成充分证明了该通用方案的有效性。
• Electrochemical nickel-catalyzed Migita cross-coupling of 1-thiosugars with aryl, alkenyl and alkynyl bromides
  作者：Mingxiang Zhu、Mouad Alami、Samir Messaoudi

  DOI：10.1039/d0cc01126f

  日期：——

  Here we report a simple route towards the synthesis of thioglycosides, in which electrochemical cross-coupling is used to form a S-C glycosidic bond from protected and unprotected thiosugars with functionalized aryl bromides under base free conditions. The reaction manifold that we report here demonstrates the power of electrochemistry to access highly complex glycosides under mild conditions.

  在这里，我们报告了一种简单的合成硫糖苷的方法，其中电化学交叉偶联用于在无碱条件下由受保护和未受保护的硫糖与功能化的芳基溴化物形成SC糖苷键。我们在此报告的反应歧管证明了在温和条件下电化学作用可获取高度复杂的糖苷的能力。
• Syntheses of cellotriose and cellotetraose analogues as transition state mimics for mechanistic studies of cellulases
  作者：Shogo Noguchi、Shintaro Takemoto、Shun-ichi Kidokoro、Kazunori Yamamoto、Masaru Hashimoto

  DOI：10.1016/j.bmc.2011.04.048

  日期：2011.6

  Cellotriose and cellotetraose analogues carrying cyclohexene rings were developed as molecular probes which are expected to mimic the transition state conformation of hydrolysis by cellulases. The cyclohexene ring was placed at the pyranose ring being expected to locate the −1 subsite of the enzyme. In order to evaluate these probes, sulfur derivatives of cellotriose and cellotetraose were also synthesized

  带有环己烯环的纤维三糖和纤维四糖类似物被开发为分子探针，有望模拟纤维素酶水解的过渡态构象。将环己烯环置于吡喃糖环上，预期其位于酶的-1个亚位点。为了评估这些探针，还合成了纤维三糖和纤维四糖的硫衍生物作为模拟天然纤维素稳定构象的耐酶类似物。使用差示扫描量热法的结合测定法表明，引入环己烯环对于与来自腐质霉（Humicola insolens）的内切葡聚糖酶NCE5的络合是有效的。
• Reversing Reactivity: Stereoselective Desulfurative 1,2-<i>trans</i>-<i>O</i>-Glycosylation of Anomeric Thiosugars with Carboxylic Acids under Copper or Cobalt Catalysis
  作者：Nedjwa Bennai、Amélie Chabrier、Maha I. Fatthalla、Christine Tran、Expédite Yen-Pon、Mohamed Belkadi、Mouâd Alami、Laurence Grimaud、Samir Messaoudi

  DOI：10.1021/acs.joc.0c00766

  日期：2020.7.17

  We have discovered a new mode of reactivity of 1-thiosugars in the presence of Cu(II) or Co(II) for a stereoselective O-glycosylation reaction. The process involves the use of a catalytic amount of Cu(acac)2 or Co(acac)2 and Ag2CO3 as an oxidant in α,α,α-trifluorotoluene. Moreover, this protocol turned out to have a broad scope, allowing the preparation of a wide range of complex substituted O-glycoside

  我们已经发现在立体选择性O-糖基化反应的Cu（II）或Co（II）存在下1-硫糖的反应性的新模式。该方法涉及使用催化量的Cu（acac）2或Co（acac）2和Ag 2 CO 3作为α，α，α-三氟甲苯中的氧化剂。而且，该方案证明具有广泛的范围，允许以良好的至优异的产率和排他的1,2-反式选择性制备多种复杂的取代的O-糖苷酯。还证明了通过这种方法对药物进行后期修饰。为了更深入地了解反应机理，进行了循环伏安法。
• Folding control of a non-natural glycopeptide using saccharide-coded structural information for polypeptides
  作者：Yuki Ishido、Naoya Kanbayashi、Naoka Fujii、Taka-aki Okamura、Takeharu Haino、Kiyotaka Onitsuka

  DOI：10.1039/c9cc10030j

  日期：——

  structure significantly changes depending on the kind of saccharide in their side chain. The saccharide moiety interacts with the main chain via hydrogen bonding, and the non-natural polypeptides form two well-defined architectures-(P)-31- and (M)-41-helices-depending on the length of the saccharide chains and even the configuration of a single stereo-genic center in the epimers.

  我们合成了“糖-脂肽”，其折叠结构根据其侧链糖的种类而显着变化。糖部分通过氢键与主链相互作用，并且非天然多肽根据糖链的长度甚至均匀地形成两个定义明确的结构-（P）-31-和（M）-41-螺旋差向异构体中单个立体基因中心的构型。