phenyl 2,3,4-tri-O-benzoyl-6-O-(2-deoxy-3,4,6-tri-O-benzyl-α-D-lyxo-hexapyranosyl)-β-D-thioglucopyranoside | 1401954-92-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,4-tri-O-benzoyl-6-O-(2-deoxy-3,4,6-tri-O-benzyl-α-D-lyxo-hexapyranosyl)-β-D-thioglucopyranoside
• 英文别名: Bn(-3)[Bn(-4)][Bn(-6)]2-deoxy-D-lyxHex(a1-6)[Bz(-2)][Bz(-3)][Bz(-4)]Glc(b)-SPh；[(2R,3R,4S,5R,6S)-4,5-dibenzoyloxy-2-[[(2S,4R,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxymethyl]-6-phenylsulfanyloxan-3-yl] benzoate
• CAS: 1401954-92-4
• 化学式: C₆₀H₅₆O₁₂S
• 分子量: 1001.16
• InChiKey: VORJADAUXIHKNV-DJIIAAFGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.4
• 重原子数：
  73
• 可旋转键数：
  24
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  160
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4-tri-O-benzoyl-6-O-(2-deoxy-3,4,6-tri-O-benzyl-α-D-lyxo-hexapyranosyl)-β-D-thioglucopyranoside 、 双丙酮半乳糖 在 N-碘代丁二酰亚胺 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以333 mg的产率得到6-(2,3,4-tri-O-benzoyl-6-O-(3,4,6-tri-O-benzyl-α-D-lyxo-hexapyranosyl)-β-D-glucopyranosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside
  参考文献：
  名称：

  α-Selective Organocatalytic Synthesis of 2-Deoxygalactosides

  摘要：

  Alpha rules: A thiourea acts as an efficient organocatalyst for the glycosylation of protected galactals to form oligosaccharides containing a 2-deoxymonosaccharide moiety. The reaction is highly stereoselective for α-linkages and proceeds by way of a syn-addition mechanism.

  DOI：

  10.1002/anie.201204505
• 作为产物：
  描述：

  (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-(phenylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetate 在 咪唑 、 4-二甲氨基吡啶 、 1,3-双[3,5-双(三氟甲基)苯基]硫脲 、 水 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 80.0h， 生成 phenyl 2,3,4-tri-O-benzoyl-6-O-(2-deoxy-3,4,6-tri-O-benzyl-α-D-lyxo-hexapyranosyl)-β-D-thioglucopyranoside
  参考文献：
  名称：

  α-Selective Organocatalytic Synthesis of 2-Deoxygalactosides

  摘要：

  Alpha rules: A thiourea acts as an efficient organocatalyst for the glycosylation of protected galactals to form oligosaccharides containing a 2-deoxymonosaccharide moiety. The reaction is highly stereoselective for α-linkages and proceeds by way of a syn-addition mechanism.

  DOI：

  10.1002/anie.201204505

文献信息

• Gold(I)-Catalyzed Direct Stereoselective Synthesis of Deoxyglycosides from Glycals
  作者：Carlos Palo-Nieto、Abhijit Sau、M. Carmen Galan

  DOI：10.1021/jacs.7b08898

  日期：2017.10.11

  AgOTf enables the unprecedented direct and α-stereoselective catalytic synthesis of deoxyglycosides from glycals. Mechanistic investigations suggest that the reaction proceeds via Au(I)-catalyzed hydrofunctionalization of the enol ether glycoside. The room temperature reaction is high yielding and amenable to a wide range of glycal donors and OH nucleophiles.

  Au（I）与AgOTf结合使用可实现前所未有的直接和直接的α-立体选择性催化合成葡萄糖脱氧糖苷的作用。机理研究表明，该反应通过Au（I）催化的烯醇醚糖苷的加氢官能​​化而进行。室温反应是高产率的，并且适用于广泛的糖基供体和OH亲核试剂。
• Copper Reactivity Can Be Tuned to Catalyze the Stereoselective Synthesis of 2-Deoxyglycosides from Glycals
  作者：Carlos Palo-Nieto、Abhijit Sau、Robin Jeanneret、Pierre-Adrien Payard、Aude Salamé、Maristela Braga Martins-Teixeira、Ivone Carvalho、Laurence Grimaud、M. Carmen Galan

  DOI：10.1021/acs.orglett.9b04525

  日期：2020.3.6

  We demonstrate that tuning the reactivity of Cu by the choice of oxidation state and counterion leads to the activation of both "armed" and "disarmed" type glycals toward direct glycosylation leading to the α-stereoselective synthesis of deoxyglycosides in good to excellent yields. Mechanistic studies show that CuI is essential for effective catalysis and stereocontrol and that the reaction proceeds

  我们证明，通过选择氧化态和抗衡离子来调节Cu的反应性会导致“武装”和“解除武装”型糖类朝着直接糖基化的活化，从而导致以良好的优良收率合成脱氧糖苷的α-立体选择性合成。机理研究表明，CuI对于有效催化和立体控制至关重要，并且该反应通过烯醇醚和OH亲核试剂的双重活化而进行。
• Copper-Catalyzed Stereoselective Synthesis of 2-Deoxygalactosides
  作者：Jianbo Zhang、Youxian Dong、Madina Yuma、Yuling Mei、Nan Jiang、Guofang Yang、Zhongfu Wang

  DOI：10.1055/s-0040-1707098

  日期：2020.7

  acids, sugars, and phenol, and proceeds with excellent yield and high α-selectivity under mild conditions. The reaction proceeds readily on a gram scale, and its versatility is exemplified in the synthesis of oligosaccharides.

  开发了一种基于 Cu(II) 催化反应合成 2-脱氧-O-半乳糖苷的有效糖基化方法，无需额外配体。糖基化适用于不同的受保护糖基供体和广泛的受体，包括醇、氨基酸、糖和苯酚，并且在温和条件下以优异的收率和高α-选择性进行。该反应在克级规模上很容易进行，其多功能性体现在低聚糖的合成中。
• Palladium‐Catalyzed Direct Stereoselective Synthesis of Deoxyglycosides from Glycals
  作者：Abhijit Sau、Ryan Williams、Carlos Palo‐Nieto、Antonio Franconetti、Sandra Medina、M. Carmen Galan

  DOI：10.1002/anie.201612071

  日期：2017.3.20

  in combination with a monodentate phosphine ligand enables the unprecedented direct and α‐stereoselective catalytic synthesis of deoxyglycosides from glycals. Initial mechanistic studies suggest that in the presence of N‐phenyl‐2‐(di‐tert‐butylphosphino)pyrrole as the ligand, the reaction proceeds via an alkoxy palladium intermediate that increases the proton acidity and oxygen nucleophilicity of the

  钯(II)与单齿膦配体相结合，能够以前所未有的方式直接和α-立体选择性催化从糖醛合成脱氧糖苷。初步机理研究表明，在N-苯基-2-(二叔丁基膦基)吡咯作为配体存在的情况下，反应通过烷氧基钯中间体进行，该中间体增加了醇的质子酸性和氧亲核性。该方法通过广泛的糖供体和受体进行了验证，包括带有烯烃官能团的底物。
• Fe(III)-catalyzed stereoselective synthesis of deoxyglycosides using stable bifunctional deoxy-phenylpropiolate glycoside donors
  作者：Anjali Aghi、Sankar Sau、Amit Kumar

  DOI：10.1016/j.carres.2024.109051

  日期：2024.2

  Herein, we report a mild and economical route for the stereoselective synthesis of 2-deoxy and 2,6-dideoxyglycosides FeCl-catalyzed activation of bench stable deoxy-phenylpropiolate glycosyl donors (D-PPGs). Optimized reaction conditions work well under additive-free conditions to afford the corresponding 2-deoxy and 2,6-dideoxyglycosides in good yields with high α-anomeric selectivity by reacting

  在此，我们报道了一种温和且经济的路线，用于立体选择性合成 2-脱氧和 2,6-二脱氧糖苷 FeCl 催化活化工作台稳定的脱氧苯丙炔酸糖基供体 (D-PPG)。优化的反应条件在无添加剂的条件下运行良好，通过与糖和非糖基受体反应，以良好的收率和高 α-异头选择性提供相应的 2-脱氧和 2,6-二脱氧糖苷。优化的条件也适用于解除武装的 D-PPG 捐赠者。此外，所开发的策略适合大规模合成。