benzyl 2,3,4,6-tetra-O-benzyl-β-D-mannopyranoside | 89615-40-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzyl 2,3,4,6-tetra-O-benzyl-β-D-mannopyranoside
• 英文别名: benzyl 2,3,4,6-tetra-O-benzyl-β-mannopyranoside；1,2,3,4,6-penta-O-benzyl-β-D-mannopyranose；benzyl 2,3,4,6-tetra-O-benzyl-beta-mannopyranoside；(2R,3S,4S,5R,6R)-2,3,4,5-tetrakis(phenylmethoxy)-6-(phenylmethoxymethyl)oxane
• CAS: 89615-40-7
• 化学式: C₄₁H₄₂O₆
• 分子量: 630.781
• InChiKey: DGGSYWYWUWWYJA-NEJZJLHVSA-N

物化性质

• 沸点：
  725.1±60.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  47
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  benzyl 2,3,4,6-tetra-O-benzyl-β-D-mannopyranoside 在 三氟甲磺酸三甲基硅酯 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 benzyl 2,3,4-tri-O-benzyl-β-D-mannopyranoside
  参考文献：
  名称：

  An expedient synthesis of benzyl 2,3,4-tri-O-benzyl-β-d-glucopyranoside and benzyl 2,3,4-tri-O-benzyl-β-d-mannopyranoside

  摘要：

  An efficient three-step synthesis of benzyl 2,3,4-tri-O-benzyl-beta-D-glucopyranoside, a widely used building block in carbohydrate chemistry, is described. The key step is the selective debenzylation-acetylation of perbenzylated beta-glucose using ZnCl2-Ac2O-HOAc. This approach was also used to affect an efficient three-step synthesis of benzyl 2,3,4-tri-O-benzyl-beta-D-mannopyranoside. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2005.02.013
• 作为产物：
  描述：

  (pent-4′-enyl) 2,3,4,6-tetra-O-benzyl-α-D-mannopyranoside 在 bromodiethylsulfonium bromopentachloroantimonate 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 反应 2.25h， 生成 benzyl 2,3,4,6-tetra-O-benzyl-β-D-mannopyranoside
  参考文献：
  名称：

  使用溴二乙基锍盐作为活化剂进行正戊烯基糖苷的糖基化：通过氯离子转移拦截糖基中间体

  摘要：

  正戊烯基糖苷（NPG）在现代碳水化合物合成中的利用可能会因其缓慢的活化而受到阻碍，这是由可逆的卤化和环化过程造成的。溴二乙基锍溴五氯锑酸盐 (BDSB) 先前已被证明是一种强大的溴化剂，可用于低反应性和缺电子多烯的阳离子-π 多烯环化。本研究展示了使用 BDSB 作为强大的溴化剂来激活 NPG。 BDSB 有效激活 NPG 的末端烯烃，反应通过 5- exo -tet 环化进行，为多种糖基供体（包括正戊烯基甘露糖苷、正戊烯基半乳糖苷和正戊烯基半乳糖苷）的糖基化提供了快速、温和的方法。戊烯基葡萄糖苷。这种方法的成功源于氯离子从非亲核 SbCl 5 Br 阴离子转移到糖基中间体，这破坏了平衡并产生糖基氯中间体，该中间体顺利转化为 22 种偶联产物，产率从中等到优异（ 49–100%）。当使用配备有邻近参与基团的 NPG 时，可以完成 β-选择性糖基化。克级合成证明了 BDSB 激活糖基化的实用性。这项研究表明

  DOI：

  10.1039/d3ob01618h

文献信息

• Electron-deficient pyridinium salts/thiourea cooperative catalyzed <i>O</i>-glycosylation via activation of <i>O</i>-glycosyl trichloroacetimidate donors
  作者：Mukta Shaw、Yogesh Kumar、Rima Thakur、Amit Kumar

  DOI：10.3762/bjoc.13.236

  日期：——

  The glycosylation of O-glycosyl trichloroacetimidate donors using a synergistic catalytic system of electron-deficient pyridinium salts/aryl thiourea derivatives at room temperature is demonstrated. The acidity of the adduct formed by the 1,2-addition of alcohol to the electron-deficient pyridinium salt is increased in the presence of an aryl thiourea derivative as an hydrogen-bonding cocatalyst. This

  证明了在室温下使用缺电子的吡啶鎓盐/芳基硫脲衍生物的协同催化系统对O-糖基三氯乙酰基亚氨酸酯供体的糖基化作用。在芳基硫脲衍生物作为氢键合助催化剂的存在下，由醇向缺电子的吡啶鎓盐的1,2-加成形成的加合物的酸度增加。这种转化在温和的反应条件下进行，反应条件与各种O-糖基三氯乙酰亚氨酸酯供体和糖基受体结合，以中等到良好的产率提供了可预测的选择性的相应O-糖苷。另外，通过使用部分保护的受体，优化的方法也用于区域选择性的O-糖基化。
• One-pot synthesis of hexias (6-O-acryl) cyclodextrin derivatives at room temperature
  作者：Yanli Cui、Shanshan Xu、Jianwei Mao

  DOI：10.1007/s10847-015-0505-z

  日期：2015.10

  A mild one-pot synthesis of hexias (6-O-acryl) cyclodextrin derivatives from per-O-benzyl-cyclodextrin was described. It was at room temperature that a regioselective conversion from benyl groups on the primary rim of cyclodextrin to the corresponding acryl groups was achieved with BF3·Me2O as catalyst and acrylic anhydride or acrylic chloride as acylating agent. The reaction was successfully applied in 6-O-acryl regioselective introduction from benzyl 2,3,4,6-tetra-O-benzyl-β-mannopyranoside as well. The products obtained can be valuable precursors for the thiol–ene click reaction or other further modification of carbohydrates.

  描述了一种温和的一锅法合成六元环糊精衍生物的方法，该方法从全-O-苄基环糊精出发，在室温下以BF3·Me2O为催化剂，丙烯酸酐或丙烯酰氯为酰化剂，实现了环糊精初级边缘苄基向相应丙烯酰基的选择性转化。该反应也成功应用于从苄基-2,3,4,6-四-O-苄基-β-甘露吡喃糖苷出发的6-O-丙烯酰基选择性引入。所得产物可作为巯基-烯点击反应或其他碳水化合物进一步修饰的有价值的中间体。
• Strained olefin enables triflic anhydride mediated direct dehydrative glycosylation
  作者：Guohua Chen、Qiang Yin、Jian Yin、Xiangying Gu、Xiao Liu、Qidong You、Yue-Lei Chen、Bing Xiong、Jingkang Shen

  DOI：10.1039/c4ob01807a

  日期：——

  Tf₂O mediated dehydrative glycosylation was enabled by strained olefins, including beta-(−)-pinene, and inhibited by other typical bases.

  Tf₂O介导的脱水糖基化反应是由受限烯烃实现的，包括β-(−)-蒎烯，并受到其他典型碱的抑制。
• A Novel Selectfluor-Mediated Regioselective <i>O</i>-Benzyl Ether Acetolysis of Perbenzylated Monosaccharides
  作者：Marlon S. Tambie、Nigel Kevin Jalsa

  DOI：10.1080/07328303.2015.1108423

  日期：2015.11.22

  Selectfluor, a source of the super electrophile F+, has replaced conventional reagents that supply F+ for fluorination due to its attractive physical and chemical properties. This study is the first report of using Selectfluor as a debenzylating reagent. Selectfluor has been found to effect regioselective O- benzyl acetolysis from the per-O-benzylated derivatives of glucose and mannose, which are among the most commonly occurring monosaccharides. For both derivatives, one equivalent of Selectfluor first cleaves the primary benzyl, while a second equivalent subsequently removes the anomeric benzyl. Regioselective removal at higher equivalents proved difficult, with complex mixtures being obtained. The reaction proceeded under mild conditions with good yields and high regioselectivity, resulting in quick access to partially benzylated monosaccharide derivatives. This study provides shortened access to attractive building blocks for oligosaccharide synthesis.
• Direct Glycosylation of Bioactive Small Molecules with Glycosyl Iodide and Strained Olefin as Acid Scavenger
  作者：Xiangying Gu、Lin Chen、Xin Wang、Xiao Liu、Qidong You、Wenwei Xi、Li Gao、Guohua Chen、Yue-Lei Chen、Bing Xiong、Jingkang Shen

  DOI：10.1021/jo402551x

  日期：2014.2.7

  A new strategy for diversity-oriented direct glycosylation of bioactive small molecules was developed. This reaction features (-)-beta-pinene as acid scavenger and work with glycosyl iodides under mild conditions. With the aid of RP-HPLC and chiral SFC separation techniques, the new direct glycosylation proved effective at gram scale on bioactive small molecules including AZD6244, podophyllotoxin, paclitaxel, and docetaxel. Interesting glycoside derivatives were efficiently created with good yields and 1,2-cis selectivity.