methyl 3-O-benzyl-2-O-(2-deoxy-3,4,6-tri-O-benzyl-α-D-lyxo-hexapyranosyl)-4,6-O-benzylidene-α-D-glucopyranoside | 1401954-88-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-O-benzyl-2-O-(2-deoxy-3,4,6-tri-O-benzyl-α-D-lyxo-hexapyranosyl)-4,6-O-benzylidene-α-D-glucopyranoside
• 英文别名: methyl 3-O-benzyl-2-O-(2-deoxy-3,4,6-tri-O-benzyl-α-D-lyxohexapyranosyl)-4,6-O-benzylidene-α-D-glucopyranoside；methyl 3-O-benzyl-2-O-(3,4,6-tri-O-benzyl-α-D-lyxo-hexapyranosyl)-4,6-O-benzylidene-α-D-glucopyranoside
• CAS: 1401954-88-8
• 化学式: C₄₈H₅₂O₁₀
• 分子量: 788.935
• InChiKey: UZMGDOOZERXDMB-CAUIMVABSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.95
• 重原子数：
  58.0
• 可旋转键数：
  17.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  92.3
• 氢给体数：
  0.0
• 氢受体数：
  10.0

反应信息

• 作为产物：
  描述：

  苯甲醛二甲缩醛 在 咪唑 、 三乙基硅烷 、 1,3-双[3,5-双(三氟甲基)苯基]硫脲 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 49.5h， 生成 methyl 3-O-benzyl-2-O-(2-deoxy-3,4,6-tri-O-benzyl-α-D-lyxo-hexapyranosyl)-4,6-O-benzylidene-α-D-glucopyranoside
  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

• Stereoselective organocatalyzed glycosylations – thiouracil, thioureas and monothiophthalimide act as Brønsted acid catalysts at low loadings
  作者：G. A. Bradshaw、A. C. Colgan、N. P. Allen、I. Pongener、M. B. Boland、Y. Ortin、E. M. McGarrigle

  DOI：10.1039/c8sc02788a

  日期：——

  Thiouracil catalyzes stereoselective glycosylations with galactals in loadings as low as 0.1 mol%.

  硫尿嘧啶在载体负载量低至0.1 mol％时，催化与半乳糖醛糖苷的立体选择性糖基化。
• Iridium-promoted deoxyglycoside synthesis: stereoselectivity and mechanistic insight
  作者：Kumar Bhaskar Pal、Aoxin Guo、Mrinmoy Das、Jiande Lee、Gábor Báti、Benjamin Rui Peng Yip、Teck-Peng Loh、Xue-Wei Liu

  DOI：10.1039/d0sc06529c

  日期：——

  devised a method for stereoselective O-glycosylation using an Ir(I)-catalyst which enables both hydroalkoxylation and nucleophilic substitution of glycals with varying substituents at the C3 position. In this transformation, 2-deoxy-α-O-glycosides were acquired when glycals equipped with a notoriously poor leaving group at C3 were used; in contrast 2,3-unsaturated-α-O-glycosides were produced from glycals

  在本文中，我们设计了一种使用Ir（I）催化剂进行立体选择性O-糖基化的方法，该方法能够在C3位置使用不同的取代基进行糖的加氢烷氧基化和亲核取代。在该转化中，当使用在C3处带有一个臭名昭著的离去基团的糖时，获得了2-脱氧-α- O-糖苷。相反，由在C3具有良好离去基团的糖基产生2，3-不饱和-α - O-糖苷。机制研究表明，这两个反应进行经由所述引导机构，通过其受体坐标到IR（我在α-面配位Ir）的金属（我）-糖基π-复合物，然后以顺式加成方式攻击包含O-糖苷键的糖基。该方案表现出良好的官能团耐受性，并以中等至高收率和优异的立体选择性制备寡糖文库为例。
• Substrate-Controlled Direct α-Stereoselective Synthesis of Deoxyglycosides from Glycals Using B(C₆F₅)₃ as Catalyst
  作者：Abhijit Sau、Carlos Palo-Nieto、M. Carmen Galan

  DOI：10.1021/acs.joc.8b02613

  日期：2019.3.1

  α-stereoselective synthesis of deoxyglycosides from glycals. 2,3-Unsaturated α- O-glycoside products are obtained with deactivated glycals at 75 °C in the presence of the catalyst, while 2-deoxyglycosides are formed using activated glycals that bear no leaving group at C-3 at lower temperatures. The reaction proceeds in good to excellent yields via concomitant borane activation of glycal donor and nucleophile

  B（C6F5）3使无金属的空前的基质控制的从糖类中脱氧糖苷的直接α-立体选择性合成成为可能。在催化剂存在下，在75°C下用失活的糖类获得2,3-不饱和α-O-糖苷产物，而使用在较低温度下C-3上不带有离去基团的活化的糖类形成2-脱氧糖苷。通过硼供体的糖基供体和亲核体受体的活化，该反应以良好的收率很好地进行。该方法以一系列稀有和生物学上相关的糖苷类似物的合成为例。
• 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。