methyl 2-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside
• 英文别名: (4Ar,6S,7R,8S,8aS)-6-methoxy-2-phenyl-7-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-ol
• 化学式: C₂₁H₂₄O₆
• 分子量: 372.418
• InChiKey: FYUXMZUFURHCOX-XLSXTYDTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside 在 palladium on activated charcoal 盐酸 、 硫酸 、 氢气 、 sodium hydride 、 溶剂黄146 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 20.0 ℃ 、506.62 kPa 条件下， 反应 36.0h， 生成 1,2,4,6-tetra-O-acetate-2-O-methyl-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of Monomethyl Derivatives ofP-Nitrophenyl α-D-Gluco, Galacto, and Mannopyranosides and their Hydrolytic Properties Against α-Glycosidases

  摘要：

  All possible monomethyl derivatives of p-nitrophenyl alpha-D-gluco, galacto, and mannopyranosides were synthesized. Hydrolytic activities of alpha-glucosidase (rice), alpha-galactosidases (green coffee bean, Mortierella vinacea, and Aspergillus niger), and alpha-mannosidases (almond and jack bean) against them were elucidated. The 6-O-methyl galactopyranoside and mannopyranoside were hydrolyzed by the M. vinacea alpha-galactosidase and the almond and jack bean alpha-mannosidases, respectively, while these enzymes did not act on the 2-, 3-, and 4-O-methyl derivatives. On the other hand, lice alpha-glucosidase and green coffee bean and A. niger alpha-galactosidases had no hydrolyzing activities at all against the respective four monomethylated substrates.

  DOI：

  10.1080/07328300008544084
• 作为产物：
  描述：

  alpha-甲基葡萄糖甙 在 四丁基硫酸氢铵 、 sodium hydride 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 17.0h， 生成 methyl 2-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Co 2（CO）6-炔丙基阳离子通过使用硫代糖苷介导糖基化反应

  摘要：

  我们发现钴-炔丙基阳离子可以通过激活硫糖苷供体来介导糖基化反应。糖-氧杂碳鎓阳离子是通过将硫代糖苷配基转移到钴-炔丙基阳离子上而形成的，该钴-炔丙基阳离子是通过用路易斯酸活化就地从钴-炔丙基化的受体生成的。供体的反应性（武装或解除武装）和路易斯酸的量控制着钴炔丙基的释放速率。

  DOI：

  10.1016/j.tetlet.2017.05.012

文献信息

• Stereoselective Glycosylation Reactions
  申请人：Trustees of Tufts College

  公开号：US20140303359A1

  公开（公告）日：2014-10-09

  Disclosed is a method for selective synthesis of 1,2-cis-α-linked glycosides which does not require the use of the specialized protecting group patterns normally employed to control diastereoselectivity. Thioglycoside acceptors can be used, permitting iterative oligosaccharide synthesis. The approach eliminates the need for lengthy syntheses of monosaccharides possessing highly specialized and unconventional protecting group patterns.

  揭示了一种选择性合成1,2-顺式α-连接的糖苷的方法，该方法不需要通常用于控制对映选择性的专门保护基团模式。可以使用硫代糖苷受体，从而允许进行寡糖合成。该方法消除了需要合成具有高度专门化和非常规保护基团模式的单糖的冗长合成过程。
• Exploring Glycosylation Reactions under Continuous-Flow Conditions
  作者：Luigi Lay、Damiano Cancogni

  DOI：10.1055/s-0034-1379471

  日期：——

  synthesis. The practical advantages of continuous-flow synthesis in microreactors (high reproducibility, easy scalability, and fast reaction optimization) may offer an effective support to make carbohydrates more attractive targets for drug-discovery processes. Here we report a systematic exploration of the glycosylation reaction carried out under microfluidic conditions. Trichloroacetimidates and

  低聚糖合成中固有的典型挑战极大地阻碍了基于碳水化合物的药物的工业发展。微反应器中连续流动合成的实际优势（高重现性、易扩展性和快速反应优化）可能为使碳水化合物成为药物发现过程中更具吸引力的目标提供有效支持。在这里，我们报告了在微流体条件下进行的糖基化反应的系统探索。三氯乙酰亚胺酯和硫糖苷已被研究作为糖基供体，使用一级和二级受体。每个微流体糖基化都与相应的分批反应进行了比较，以突出微反应器技术的优缺点。
• Catalytic activation of glycosyl phosphates for stereoselective coupling reactions
  作者：Samuel M. Levi、Qiuhan Li、Andreas R. Rötheli、Eric N. Jacobsen

  DOI：10.1073/pnas.1811186116

  日期：2019.1.2

  Glycosyl phosphates are shown to be activated to stereospecific nucleophilic substitution reactions by precisely tailored bis-thiourea catalysts. Enhanced reactivity and scope is observed with phosphate relative to chloride leaving groups. Stronger binding (Km) to the H-bond donor and enhanced reactivity of the complex (kcat) enables efficient catalysis with broad functional group compatibility under

  糖基磷酸酯已显示通过精确定制的双硫脲催化剂被激活成立体定向亲核取代反应。相对于氯化物离去基团，磷酸盐具有增强的反应性和范围。与氢键供体的更强结合（K m）和配合物（k cat）的增强的反应性可在温和，中性条件下以广泛的官能团相容性实现高效催化。
• Reactions of relevance to the chemistry of aminoglycoside antibiotics. Part 13. A novel synthesis of benzyl ethers
  作者：Anthony G. M. Barrett、Roger W. Read、Derek H. R. Barton

  DOI：10.1039/p19800002184

  日期：——

  Benzyl ethers were prepared from alcohols by reaction with chloro(phenylmethylene)dimethylammonium chloride and sodium hydrogen telluride in sequence. The salt (1)[Me2NC(R1)OR2Cl–; R1= H, R2= cholest-5-en-3β-yl] and sodium borohydride gave the borane complex of 3β-dimethylaminomethoxycholest-5-ene. Salt (1; R1= Ph, R2= cholest-5-en-3β-yl or 5α-cholestan-3β-yl) and ammonia or hydrazine gave the steroidal

  通过依次与氯（苯基亚甲基）二甲基氯化铵和碲化氢钠反应，由醇制得苄基醚。盐（1）[我2 NC（R 1）OR 2氯- ; R 1＝ H，R 2＝胆甾-5-烯-3β-基]，硼氢化钠得到3β-二甲基氨基甲氧基胆甾-5-烯的硼烷配合物。盐（1； R 1 = Ph，R 2 =胆甾-5-en-3β-基或5α-胆甾-3β-基）和氨或肼得到甾族苯甲酸酯或苯甲酰肼酸盐。
• Additive‐Free Gold(III)‐Catalyzed Stereoselective Synthesis of 2‐Deoxyglycosides Using Phenylpropiolate Glycosides as Donors
  作者：Mukta Shaw、Amit Kumar

  DOI：10.1002/asia.201900888

  日期：2019.12.13

  Stereoselective synthesis of deoxyglycosides has been achieved from benchtop stable and easily synthesizable deoxy-phenylpropiolate glycosides (D-PPGs) using gold(III) salt as catalyst under external additive-free conditions. Under a simple catalytic system, D-PPGs reacted with a variety of sugar and non-sugar acceptors to produce majorly α-stereoselective O/N-deoxyglycosides in good to excellent yields

  在无外部添加剂的条件下，使用金（III）盐作为催化剂，可从台式稳定且易于合成的脱氧苯丙酸丙二醇酯（D-PPGs）中实现脱氧糖苷的立体选择性合成。在简单的催化系统下，D-PPG与多种糖和非糖受体反应，以高至优异的收率产生主要的α-立体选择性O / N-脱氧糖苷，并再生易于分离和重用的苯丙酸。在优化的反应条件下，含有武装和解除武装团体的脱氧PPG能够很好地存活。另外，展示了D-PPG的正交性质，并且还合成了1，1'-连接的海藻糖型糖。