phenyl 4,6-O-benzylidene-2,3-di-O-methyl-1-thio-β-D-glucopyranose | 161391-28-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 4,6-O-benzylidene-2,3-di-O-methyl-1-thio-β-D-glucopyranose
• 英文别名: (2R,4aR,6S,7R,8S,8aR)-7,8-dimethoxy-2-phenyl-6-phenylsulfanyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• CAS: 161391-28-2
• 化学式: C₂₁H₂₄O₅S
• 分子量: 388.485
• InChiKey: JKQSNRUQMPCBQH-RZTRGMPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 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：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 4,6-O-benzylidene-2,3-di-O-methyl-1-thio-β-D-glucopyranose 在 吡啶 、 4-二甲氨基吡啶 、 Grubbs catalyst first generation 、 sodium azide 、 15-冠醚-5 、 D(+)-10-樟脑磺酸 、 水 、 四丁基碘化铵 、 sodium hydride 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 212.33h， 生成 (E)-(2S,3R,4S,4aR,15aR)-3,4-Dimethoxy-2-phenylsulfanyl-3,4,4a,7,8,11,12,14,15,15a-decahydro-2H,6H-1,5-dioxa-14-aza-benzocyclotridecen-13-one
  参考文献：
  名称：

  A Convergent Ring-Closing Metathesis Approach to Carbohydrate-Based Macrolides with Potential Antibiotic Activity

  摘要：

  An efficient convergent approach has been developed for the construction of novel, non-natural, carbohydrate-based macrolides. The key step in the synthesis is the formation of the macrocyclic ring via a ring-closing metathesis reaction. The obtained macrolide analogues have been screened for biological activity against, Gram-positive and Gram-negative bacteria, including resistant strains, yeasts, and molds.

  DOI：

  10.1021/jo051021k
• 作为产物：
  描述：

  苯基-4,6-O-苯亚甲基-1-硫代-Β-D-吡喃葡萄糖苷 、 碘甲烷 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以97%的产率得到phenyl 4,6-O-benzylidene-2,3-di-O-methyl-1-thio-β-D-glucopyranose
  参考文献：
  名称：

  通过2- O-烷氧基甲基的相邻基团参与的1,2-反式糖基化：在一锅低聚糖合成中的应用

  摘要：

  据报道，使用2- O-烷氧基甲基作为有效的立体定向取代基来构建1，2-反式糖苷键。观察到的立体选择性来自2- O-烷氧基甲基取代基和氧碳鎓离子之间的五元环状结构的分子内形成，这提供了预期的面部选择性。此外，观察到的立体控制和2 - O-烷氧基甲基保护的供体的极高反应性允许开发一锅顺序糖基化策略，该策略应成为组装寡糖的有力工具。

  DOI：

  10.1021/acs.orglett.9b00220

文献信息

• IPy₂BF₄/HF-Pyridine:  A New Combination of Reagents for the Transformation of Partially Unprotected Thioglycosides and <i>n</i>-Pentenyl Glycosides to Glycosyl Fluorides
  作者：J. Cristóbal López、Paloma Bernal-Albert、Clara Uriel、Serafín Valverde、Ana M. Gómez

  DOI：10.1021/jo7018653

  日期：2007.12.1

  The combination of bis(pyridinium)iodonium (I) tetrafluoroborate (IPy2BF4), and hydrogen fluoride pyridine (HF-py) forms an iodine monofluoride (IF) synthetic equivalent that can be used in the preparation of partially unprotected glycosyl fluorides from partially unprotected n-pentenyl glycosides and thioglycosides, thus avoiding the need for the protection/deprotection steps normally required in

  四氟硼酸双（吡啶）碘鎓（I）（IPy 2 BF 4）和氟化氢吡啶（HF-py）的组合形成碘一氟化物（IF）合成等价物，可用于制备部分未保护的糖基氟化物部分未保护的正戊烯基糖苷和巯基糖苷，因此避免了通常需要在该转化中进行的保护/去保护步骤。
• BODIPYs as Chemically Stable Fluorescent Tags for Synthetic Glycosylation Strategies towards Fluorescently Labeled Saccharides
  作者：Clara Uriel、Caterina Permingeat、Juan Ventura、Edurne Avellanal‐Zaballa、Jorge Bañuelos、Inmaculada García‐Moreno、Ana M. Gómez、J. Cristobal Lopez

  DOI：10.1002/chem.201905780

  日期：2020.4.24

  chromophores on the ensuing compounds grants access to fluorescently labeled saccharides. In this context, a sought-after feature of the fluorescent dyes has been their chemical robustness. Accordingly, some BODIPY derivatives described in this work can withstand the reaction conditions commonly employed in the chemical synthesis of saccharides; namely, glycosylation and protecting-group manipulations. Regarding

  已经设计了一系列荧光硼-二吡咯亚甲基（BODIPY，4,4-二氟-4-硼3a，4a-二氮杂-s-茚并四烯）染料作为糖苷配基参与合成的寡糖方案。因此，它们具有双重目的：首先，通过在过程开始时（在生长的糖部分的还原端）掺入，它们可以充当荧光糖基标签，从而促进所需糖苷的检测和纯化。中间体，其次，这些发色团在随后的化合物上的存在允许获得荧光标记的糖类。在这种情况下，荧光染料的抢手特征是其化学稳定性。因此，这项工作中描述的某些BODIPY衍生物可以承受糖类化学合成中通常使用的反应条件。即糖基化和保护基操纵。关于它们的光物理性质，在这项工作中获得的BODIPY标记的糖类在水中显示出显着的荧光效率，达到高达82％的量子产率值，并且具有显着的激光效率和光稳定性。
• Stabilization of glycosyl sulfonium ions for stereoselective O-glycosylation
  作者：Lihong Sun、Pan Li、Kang Zhao

  DOI：10.1016/0040-4039(94)85346-0

  日期：1994.9

  Bis(trifluoroacetoxy)iodobenzene can be used for studying the stereoselectivity of O-glycosylation from thioglycosides and the use of reagent-stabilized sulfonium ions to prohibit the formation of oxonium ions is also discussed.

  双（三氟乙酰氧基）碘苯可用于研究硫代糖苷中O-糖基化的立体选择性，并讨论了使用试剂稳定的sulf离子来阻止氧离子的形成。
• General access to asymmetric γ-cyclodextrins for gas chromatographic applications by insertion of a selectively modified sugar unit
  作者：Eric Bourgeaux、Jean-Claude Combret

  DOI：10.1016/s0957-4166(00)00396-7

  日期：2000.10

  Gas chromatography (GC) using chiral stationary phases (CSPs) based on modified cyclodextrins is the most commonly used technique to quantify enantiomeric purity of synthesized volatile racemic drugs. The fully methylated cyclodextrin derivatives are the most used because of their easy synthesis, their thermal stability and their ability to recognize a wide range of compounds. To complete the background on molecular recognition, we describe a route to access fully characterized new asymmetric cyclodextrins derived from fully methylated ones, thereby directly useful in chiral gas chromatography. The synthesis of these compounds involves a three-step procedure: ring opening of fully methylated cyclodextrins, elongation of the chain with correctly modified monosaccharide derivatives and, finally, macrocyclization to obtain the desired compounds. This strategy is applied to achieve the synthesis of a series of asymmetric gamma -cyclodextrins, by insertion of glucopyranosic derivatives. Appropriate selection of the glycosylating reagents during chain elongation and macrocyclization steps allows satisfactory anomeric selectivities to be reached. (C) 2000 Elsevier Science Ltd. All rights reserved.
• US7534871B2
  申请人：——

  公开号：US7534871B2

  公开（公告）日：2009-05-19