2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl iodide | 250691-64-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl iodide
• 英文别名: (2R,3S,4S,5R,6R)-2-iodo-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane
• CAS: 250691-64-6
• 化学式: C₃₄H₃₅IO₅
• 分子量: 650.553
• InChiKey: JJQMCIYEJMJTFX-ZOHVZMGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  40
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  戊腈 、 2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl iodide 以 四氢呋喃 为溶剂， 生成 2,3,4,6-tetra-O-benzyl-β-D-mannopyranosyl cyanide
  参考文献：
  名称：

  Glycosyl iodides. History and recent advances

  摘要：

  The use of glycosyl iodides as an effective method for the preparation of glycosides has had a recent resurgence in carbohydrate chemistry, despite its early roots in which these species were believed to be of limited use. Renewed interest in these species as glycosylating agents has been spurred by their demonstrated utility in the stereoselective preparation of O-glycosides, and other glycosylic compounds. This review provides a brief historical account followed by an examination of the use of glycosyl iodides in the synthesis of oligosaccharicles and other glycomimetics, including C-glycosylic compounds, glycosyl azides and N-glycosides. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2009.02.032
• 作为产物：
  描述：

  伪-D-Mannopyranose,2,3,4,6-tetrakis-O-(phenylmethyl)-,acetate(9CI) 在 碘代三甲硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 0.75h， 生成 2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl iodide
  参考文献：
  名称：

  d-甘油-d-甘露聚糖-庚糖1,7-二磷酸酯的化学合成及其调节NF-κB活化能力的评估

  摘要：

  d -甘油基- d -甘露-Heptose 1,7-二磷酸（HBP）是庚糖残基的前体在革兰氏阴性细菌膜表面糖蛋白和糖脂中。最近报道，HBPβ-异头物是一种病原体相关分子模式（PAMP），可调节TIFA依赖性免疫。在这里，我们报道了HBPα-和β-端基异构体的化学合成，该反应突出了通过Corey-Chaykovsky反应的C-7碳同系物，以及使用Mitsunobu反应在端基异构体位置引入了磷酸基团。此外，NF-κB报告基因检测表明，HBPβ-异头物激活了NF-κB信号传导途径。

  DOI：

  10.1021/acs.orglett.7b01158

文献信息

• Glycosyl iodides are highly efficient donors under neutral conditions
  作者：Michael J. Hadd、Jacquelyn Gervay

  DOI：10.1016/s0008-6215(99)00146-9

  日期：1999.7

  Abstract Glycosyl iodides have been prepared and subjected to glycosylation under neutral conditions. The reactions are highly efficient, giving α glycosides even with sterically demanding glycosyl acceptors. Glucosyl iodides react with allyl alcohol slowest and require refluxing conditions. Galactosyl iodides are intermediate in reactivity, providing the allyl glycoside in 3 h at room temperature

  摘要制备了糖基碘化物并在中性条件下进行糖基化。该反应是高效的，即使具有空间上要求的糖基受体也能得到α糖苷。葡萄糖基碘与烯丙醇的反应最慢，需要回流条件。半乳糖基碘化物是反应性的中间产物，在室温下3小时内可提供烯丙基糖苷，而岩藻糖基碘化物的糖基化在相似条件下可在不到1小时内发生。用包括异头羟基在内的各种受体证明了反应的范围和局限性，得到了海藻糖类似物。在不存在C-2参与的情况下，只需将溶剂从苯改成乙腈就可以实现葡萄糖基碘化物的β-选择性糖基化。
• Mild Synthesis of Protected α-D-Glycosyl Iodides
  作者：Romualdo Caputo、Horst Kunz、Domenico Mastroianni、Giovanni Palumbo、Silvana Pedatella、Francesco Solla

  DOI：10.1002/(sici)1099-0690(199911)1999:11<3147::aid-ejoc3147>3.0.co;2-i

  日期：1999.11

  α-D-Glycosyl iodides are stereoselectively obtained by iodine replacement of the free anomeric hydroxyl group of fully protected sugars treated with a polymer bound triarylphosphane-iodine complex and imidazole. High yields and mild conditions, compatible with all the common protecting groups used in carbohydrate chemistry, characterize the conversion.

  α-D-糖基碘化物是通过碘取代用聚合物结合的三芳基膦-碘复合物和咪唑处理的完全保护的糖的游离异头羟基而立体选择性地获得的。与碳水化合物化学中使用的所有常见保护基团兼容的高产率和温和条件是转化的特征。
• Stereoselective β-mannosylations and β-rhamnosylations from glycosyl hemiacetals mediated by lithium iodide
  作者：Imlirenla Pongener、Dionissia A. Pepe、Joseph J. Ruddy、Eoghan M. McGarrigle

  DOI：10.1039/d1sc01300a

  日期：——

  Stereoselective β-mannosylation is one of the most challenging problems in the synthesis of oligosaccharides. Herein, a highly selective synthesis of β-mannosides and β-rhamnosides from glycosyl hemi-acetals is reported, following a one-pot chlorination, iodination, glycosylation sequence employing cheap oxalyl chloride, phosphine oxide and LiI. The present protocol works excellently with a wide range

  立体选择性β-甘露糖基化是寡糖合成中最具挑战性的问题之一。在此，报道了使用廉价的草酰氯、氧化膦和 LiI 进行一锅氯化、碘化、糖基化序列后，从糖基半缩醛中高度选择性地合成 β-甘露糖苷和 β-鼠李糖苷。本协议适用于广泛的糖基受体和武装糖基供体。该方法不需要构象限制的供体或导向基团；建议观察到的高β-选择性是通过碘化锂促进的 α-糖基碘化物的 S N 2 型反应实现的。
• Stereoselective Synthesis of α-Glycosyl Phosphites and Phosphoramidites via <i>O</i>-Selective Glycosylation of <i>H</i>-Phosphonate Derivatives
  作者：Fumiko Matsumura、Natsuhisa Oka、Takeshi Wada

  DOI：10.1021/ol802190x

  日期：2008.11.20

  A highly stereo- and chemoselective glycosylation of H-phosphonate derivatives with glycosyl iodides was discovered as a reverse reaction of the formation of a glycosyl iodide from a glycosyl phosphite and I- under mild acidic conditions. Further study on the unique reaction showed that the reaction provided various alpha-glycosyl phosphites; and phosphoramidites in a highly stereoselective manner with complete O-selectivity.