phenyl 2,3,6,2',3',4',5'-hepta-O-acetyl-1-thio-β-cellobioside | 28022-14-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,6,2',3',4',5'-hepta-O-acetyl-1-thio-β-cellobioside
• 英文别名: phenyl 2,3,6,2',3',4',6'-hepta-O-acetyl-1-thio-β-cellobioside；phenyl 2,3,6,2',3',4',6'-hepta-O-acetyl-1-thio-β-cellobiose；phenyl 1-thio-β-cellobioside heptaacetate；phenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranoside；p-tolyl 2,3,6-tri-O-acetyl-4-O-(2′,3′,4′,6′-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-D-glucopyranoside；phenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl-(1->4)-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranoside；phenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-D-thioglucopyranoside；2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranoside；phenyl hepta-O-acetyl-1-thio-β-D-cellobioside；phenyl-[O²,O³,O⁶-triacetyl-O⁴-(tetra-O-acetyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside]；Phenyl-[O²,O³,O⁶-triacetyl-O⁴-(tetra-O-acetyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranosid]；1-thiophenyl-2,3,6-tri-O-acetyl-4-O-(2',3',4',6'-tetra-O-acetyl-β-D-glucopyranosyl)-β-D-glucopyranoside；phenyl 2,3,6-tri-O-acetyl-β-D-glucopyranosyl-[1-4]-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranoside；Glc2Ac3Ac4Ac6Ac(b1-4)Glc2Ac3Ac6Ac(b)-SPh；[(2R,3R,4S,5R,6S)-3,4,5-triacetyloxy-6-[(2R,3R,4S,5R,6S)-4,5-diacetyloxy-2-(acetyloxymethyl)-6-phenylsulfanyloxan-3-yl]oxyoxan-2-yl]methyl acetate
• CAS: 28022-14-2
• 化学式: C₃₂H₄₀O₁₇S
• 分子量: 728.725
• InChiKey: OJVHDCHVHOISBO-CBUXPLGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  50
• 可旋转键数：
  20
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  237
• 氢给体数：
  0
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,6,2',3',4',5'-hepta-O-acetyl-1-thio-β-cellobioside 在 N-溴代丁二酰亚胺(NBS) 、 4 A molecular sieve 、 silver perchlorate 、 4,4'-二氨基二苯乙烯-2,2'-二磺酸 、 tin(ll) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 54.0h， 生成
  参考文献：
  名称：

  Stereospecific synthesis of rhynchosporosides, a family of fungal metabolites causing scald disease in barley and other grasses

  摘要：

  DOI：

  10.1021/ja00305a056
• 作为产物：
  描述：

  Cellobiose 在 三氟化硼乙醚 、 sodium acetate 作用下， 以 二氯甲烷 为溶剂， 反应 7.0h， 生成 phenyl 2,3,6,2',3',4',5'-hepta-O-acetyl-1-thio-β-cellobioside
  参考文献：
  名称：

  A study of anhydrocelluloses – Is a cellulose structure with residues in a 1C4-conformation more prone to hydrolysis?

  摘要：

  对纤维素结构中引入3,6-脱水葡萄糖残基对糖苷水解速率的影响进行了研究。合成了以3,6-脱水葡萄糖为第三残基的纤维四糖。对这种四糖进行酸性水解后发现，3,6-脱水-β-D-葡萄糖苷键的水解速度比纤维二糖的水解速度快31400倍。通过在二甲基乙酰胺中用不同量的对甲苯磺酰氯对纤维素进行对甲苯磺酰化，并随后用氢氧化钠处理，制备了一系列具有不同取代度的3,6-脱水纤维素。得到了取代度分别为0.02、0.07、0.31和0.74的脱水纤维素。在2.0 M HCl水溶液中对脱水纤维素进行酸性水解，并通过离子色谱分析生成的葡萄糖和/或纤维二糖的量来监测水解速率。所有3,6-脱水纤维素的水解速率都比纤维素快，但取代度低（ds = 0.07）的脱水纤维素水解最快，比纤维素快90倍。

  DOI：

  10.1039/c1ob06085f

文献信息

• A Generalized Procedure for the One-Pot Preparation of Glycosyl Azides and Thioglycosides Directly from Unprotected Reducing Sugars under Phase-Transfer Reaction Conditions
  作者：Rishi Kumar、Pallavi Tiwari、Prakas R. Maulik、Anup K. Misra

  DOI：10.1002/ejoc.200500646

  日期：2006.1

  Per-O-acetylated glycosyl azides and thioglycosides were prepared in excellent yield directly from unprotected reducing sugars through in situ generation of per-O-acetylated glycosyl bromides by a generalized one-pot procedure under phase-transfer conditions. Stereoselective products were formed with complete inversion at the anomeric centers of the glycosyl bromides to provide a general high-yielding

  过氧乙酰化糖基叠氮化物和硫代糖苷直接从未保护的还原糖通过通用的一锅法在相转移条件下原位生成过氧乙酰化糖基溴化物，以优异的收率制备。在糖基溴化物的异头中心完全反转形成立体选择性产物，为制备 1,2-反式糖基叠氮化物和硫代糖苷提供了一种通用的高产率方法。（© Wiley-VCH Verlag GmbH & Co. KGaA， 69451 德国魏因海姆，2006）
• Appel-reagent-mediated transformation of glycosyl hemiacetal derivatives into thioglycosides and glycosyl thiols
  作者：Tamashree Ghosh、Abhishek Santra、Anup Kumar Misra

  DOI：10.3762/bjoc.9.112

  日期：——

  A series of glycosyl hemiacetal derivatives have been transformed into thioglycosides and glycosyl thiols in a one-pot two-step reaction sequence mediated by Appel reagent (carbon tetrabromide and triphenylphosphine). 1,2-trans-Thioglycosides and β-glycosyl thiol derivatives were stereoselectively formed by the reaction of the in situ generated glycosyl bromides with thiols and sodium carbonotrithioate. The reaction conditions are reasonably simple and yields were very good.

  一系列的糖基半缩醛衍生物已经通过一锅两步反应序列（介导剂为Appel试剂（四溴化碳和三苯基膦））转化为硫代糖苷和糖基硫醇。通过原位生成的糖基溴化物与硫醇和碳硫代酸钠反应，选择性地形成了1,2-trans-硫代糖苷和β-糖基硫醇衍生物。反应条件相当简单，产率非常高。
• 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。
• Self‐Promoted Glycosylation for the Synthesis of β‐ <i>N</i> ‐Glycosyl Sulfonyl Amides
  作者：Patrycja Mała、Christian Marcus Pedersen

  DOI：10.1002/ejoc.202100808

  日期：2021.11.8

  Glycosyl sulfonyl amides are synthesized in a self-promoted N-glycosylation with high β-selectivity and in high yields. Armed and disarmed glycosyl donors of different size and with different protective groups react smoothly with sulfonyl amides, such as protected asparagine derivatives. Influence of solvents, concentration, temperature and stoichiometry is studied.

  糖基磺酰酰胺是通过自我促进的N-糖基化合成的，具有高 β-选择性和高产率。不同大小和不同保护基团的武装和解除武装的糖基供体可与磺酰胺（例如受保护的天冬酰胺衍生物）顺利反应。研究了溶剂、浓度、温度和化学计量的影响。
• Efficient one-pot per-O-acetylation–thioglycosidation of native sugars, 4,6-O-arylidenation and one-pot 4,6-O-benzylidenation–acetylation of S-/O-glycosides catalyzed by Mg(OTf)₂
  作者：Mana Mohan Mukherjee、Nabamita Basu、Aritra Chaudhury、Rina Ghosh

  DOI：10.1039/c6ra23198e

  日期：——

  A sequential one-pot per-O-acetylation–S-/O-glycosidation of native mono and disaccharides under solvent free conditions using 0.5 mole% of Mg(OTf)2 as a non-hygroscopic, recyclable catalyst is reported. Regioselective 4,6-O-arylidenation of glycosides and thioglycosides with benzaldehyde or p-methoxybenzaldehyde dimethyl acetal is catalyzed by 10 mole% of Mg(OTf)2 to produce the corresponding 4,6-O-arylidenated

  据报道，在无溶剂条件下，使用0.5摩尔％的Mg（OTf）2作为非吸湿性，可循环利用的催化剂，对单糖和双糖进行连续一锅过O-乙酰化– S- / O-糖基化反应。糖苷和硫糖苷与苯甲醛或对甲氧基苯甲醛二甲基乙缩醛的区域选择性4,6- O-芳基化反应可通过10摩尔％的Mg（OTf）2催化生成相应的4,6- O-芳基化产物。Mg（OTf）2也可以高产率地介导单糖和二糖基糖苷和硫代糖苷的顺序一锅苯甲基化-乙酰化。