[(3aS,5R,6R,7S,7aS)-6,7-dibenzoyloxy-2-phenyl-2-prop-2-enoxy-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-5-yl]methyl benzoate | 853308-55-1

• 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: [(3aS,5R,6R,7S,7aS)-6,7-dibenzoyloxy-2-phenyl-2-prop-2-enoxy-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-5-yl]methyl benzoate
• CAS: 853308-55-1
• 化学式: C₃₇H₃₂O₁₀
• 分子量: 636.655
• InChiKey: KJKRWQFTQXMXFY-SPLNREBESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  47
• 可旋转键数：
  14
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  116
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  [(3aS,5R,6R,7S,7aS)-6,7-dibenzoyloxy-2-phenyl-2-prop-2-enoxy-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-5-yl]methyl benzoate 在 氟化氢吡啶 作用下， 以 二氯甲烷 为溶剂， 以84%的产率得到2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl fluoride
  参考文献：
  名称：

  Reaction of 1,2-Orthoesters with HF−Pyridine: A Method for the Preparation of Partly Unprotected Glycosyl Fluorides and Their Use in Saccharide Synthesis

  摘要：

  Glycosyl fluorides can be prepared In an efficient manner by treatment of pyranose- or furanose-derived 1,2-orthoesters, with hydrogen fluoride pyridine (HF-py). The method is compatible with the presence of a variety of protecting groups, including tert-butyldiphenyl silyl ethers, and can be applied to sugar derivatives with free hydroxyl groups, thus avoiding the need for the protection-deprotection steps.

  DOI：

  10.1021/ol901630d
• 作为产物：
  描述：

  2,3,4,6-Tetra-O-benzoyl-α-D-mannopyranosyl bromide 、 烯丙醇 在 2,6-二甲基吡啶 、 [bmim]PF₆ 作用下， 反应 8.0h， 以90%的产率得到[(3aS,5R,6R,7S,7aS)-6,7-dibenzoyloxy-2-phenyl-2-prop-2-enoxy-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-5-yl]methyl benzoate
  参考文献：
  名称：

  A Facile and Eco-Friendly Method for the Synthesis of 1,2-Orthoesters of Carbohydrates in Ionic Liquid

  摘要：

  本文描述了一种在离子液体[bmim]PF6中合成碳水化合物1,2-邻醚的简便方法。所述方法更简单、环保，且避免了添加季铵盐作为促进剂。

  DOI：

  10.1055/s-2005-864818

文献信息

• Chemical Synthesis of All Phosphatidylinositol Mannoside (PIM) Glycans from <i>Mycobacterium tuberculosis</i>
  作者：Siwarutt Boonyarattanakalin、Xinyu Liu、Mario Michieletti、Bernd Lepenies、Peter H. Seeberger

  DOI：10.1021/ja806283e

  日期：2008.12.10

  interactions with host cells, and to investigate the function of PIMs as potential antigens and/or adjuvants for vaccine development. Here, we report the efficient synthesis of all PIMs including phosphatidylinositol (PI) and phosphatidylinositol mono- to hexa-mannoside (PIM1 to PIM6). Robust synthetic protocols were developed for utilizing bicyclic and tricyclic orthoesters as well as mannosyl phosphates

  耐多药结核病 (TB) 的出现以及用于保护人类免受结核病侵害的 BCG 结核病疫苗的问题促使人们对通过探索新的细菌药物靶点和疫苗来对抗这种疾病的替代方法进行调查。磷脂酰肌醇甘露糖苷 (PIM) 是生物学上重要的糖缀合物，代表更复杂的分枝杆菌细胞壁糖脂的常见必需前体，包括脂甘露聚糖 (LM)、脂阿拉伯甘露聚糖 (LAM) 和甘露聚糖封端的脂阿拉伯甘露聚糖 (ManLAM)。合成 PIM 是阐明此类分子的生物合成、揭示 PIM 与宿主细胞的相互作用以及研究 PIM 作为疫苗开发的潜在抗原和/或佐剂的功能的重要生化工具。这里，我们报告了所有 PIM 的有效合成，包括磷脂酰肌醇 (PI) 和磷脂酰肌醇单至六甘露糖苷 (PIM1 至 PIM6)。为利用双环和三环原酸酯以及甘露糖基磷酸酯作为糖基化剂开发了稳健的合成方案。每个合成 PIM 都配备有用于固定在表面和载体蛋白上的硫醇接头，用于生物学和免疫学研究。合成的
• A Facile and Eco-Friendly Method for the Synthesis of 1,2-Orthoesters of Carbohydrates in Ionic Liquid
  作者：K. Radhakrishnan、V. Sajisha、Jessy Chacko

  DOI：10.1055/s-2005-864818

  日期：——

  A facile method for the synthesis of 1,2-orthoesters of carbohydrates in ionic liquid [bmim]PF6 is described. The method described herein is simpler, eco-friendly and avoids the addition of quaternary ammonium salts as promoters.

  本文描述了一种在离子液体[bmim]PF6中合成碳水化合物1,2-邻醚的简便方法。所述方法更简单、环保，且避免了添加季铵盐作为促进剂。
• Ionic Liquid [bmim]PF₆-Mediated Synthesis of 1,2-Orthoesters of Carbohydrates and the Glycosidation Reactions of 4-Pentenyl Orthoesters
  作者：Saithalavi Anas、Valiyaveetil Sanjayan Sajisha、Rani Rajan、Rajasekaran Thirumalai Kumaran、Kokkuvayil Vasu Radhakrishnan

  DOI：10.1246/bcsj.80.553

  日期：2007.3.15

  A facile synthesis of the 1,2-orthoesters of carbohydrates in the ionic liquid [bmim]PF6 without a quaternary ammonium salt like tetrabutylammonium iodide, is described. The glycosidation reactions of 4-pentenyl orthoesters (NPOEs) with different alcohols are also discussed. The work described in this paper showed that [bmim]PF6 is an efficient and recyclable solvent for the synthesis and glycosidation reaction of orthoesters.

  描述了一种在离子液体[bmim]PF6中合成糖类1,2-邻醚的简便方法，无需使用四丁基氨铵盐如碘化四丁基铵。还讨论了4-戊烯基邻醚（NPOEs）与不同醇的糖苷化反应。本文所述的工作表明，[bmim]PF6是一种高效且可回收的溶剂，用于邻醚的合成和糖苷化反应。
• Unexpected Stereocontrolled Access to 1α,1′β-Disaccharides from Methyl 1,2-Ortho Esters
  作者：Clara Uriel、Juan Ventura、Ana M. Gómez、J. Cristóbal López、Bert Fraser-Reid

  DOI：10.1021/jo202335n

  日期：2012.1.6

  Mannopyranose-derived methyl 1,2-orthoacetates (R = Me) and 1,2-orthobenzoates (R = Ph) undergo stereoselective formation of 1 alpha,1'beta-disaccharides, upon treatment with BF3 center dot Et2O in CH2Cl2, rather than the expected acid-catalyzed reaction leading to methyl glycosides by way of a rearrangement-glycosylation process of the liberated methanol.
• Polymerization of mannosyl tricyclic orthoesters for the synthesis of α(1–6) mannopyranan—the backbone of lipomannan
  作者：Chanokpon Yongyat、Somsak Ruchirawat、Siwarutt Boonyarattanakalin

  DOI：10.1016/j.bmc.2010.04.014

  日期：2010.6.1

  Tuberculosis (TB) remains a major health problem worldwide. Understanding the interactions between the surface components of Mycobacterium tuberculosis (Mtb), the main causative agent of TB, with host immune response will be critical for developments of effective treatments and prevention of TB. Chemically defined mimics of the bacterial envelope components serve as important tools for biological studies of the bacterial interactions with mammalian hosts. We report here a rapid synthetic approach utilizing mannosyl tricyclic orthoesters as monomers for regio- and stereo-controlled polymerizations to generate alpha(1-6) mannopyranan-the backbone of lipomannan. The polymerizations generated multiple glycosidic bonds in a single chemical transformation in regio- and stereo-selective manners. TMSOTf is the optimum catalyst to promote the selective and high yielding polymerization when compared with other Lewis acids. In addition, the monomers 3,4-O-benzyl-beta-D-mannopyranose 1,2,6-orthobenzoate (1) and 3,4-O-benzyl-beta-D-mannopyranose 1,2,6-orthopivalate (2) can be synthesized in multiple-gram scale and in a rapid fashion. Characterizations by GPC and NMR indicate the identity of alpha(1-6) mannopyranan with DPn (degree of polymerization) = 20. (C) 2010 Elsevier Ltd. All rights reserved.