2,3:4,6-di-O-isopropylidene-D-glucopyranose

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 2,3:4,6-di-O-isopropylidene-D-glucopyranose
• 英文别名: (1R,2S,6R,9R)-4,4,12,12-tetramethyl-3,5,8,11,13-pentaoxatricyclo[7.4.0.02,6]tridecan-7-ol
• 化学式: C₁₂H₂₀O₆
• 分子量: 260.287
• InChiKey: QIFUEBARKWFBGQ-ZKZCYXTQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  2,3:4,6-di-O-isopropylidene-D-glucopyranose 在 吡啶 、 4-二甲氨基吡啶 、 selenium 、 sodium tetrahydroborate 、 三氟乙酸 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 1,5-dideoxy-5-seleno-L-iditol
  参考文献：
  名称：

  Preventing Protein Oxidation with Sugars: Scavenging of Hypohalous Acids by 5-Selenopyranose and 4-Selenofuranose Derivatives

  摘要：

  Heme peroxidases including myeloperoxidase (MPO) are released at sites of inflammation by activated leukocytes. MPO generates hypohalous acids (HOX, X = Cl, Br, SCN) from H2O2; these oxidants are bactericidal and are key components of the inflammatory response. However, excessive, misplaced or mistimed production can result in host tissue damage, with this implicated in multiple inflammatory diseases. We report here methods for the conversion of simple monosaccharide sugars into selenium- and sulfur-containing species that may act as potent water-soluble scavengers of HOX. Competition kinetic studies show that the seleno species react with HOC with rate constants in the range 0.8-1.0 X 10(8) M-1 s(-1), only marginally slower than those for the most susceptible biological targets including the endogenous antioxidant, glutathione. The rate constants for the corresponding sulfur sugars are considerably slower (1.4-1.9 X 10(6) M-1 s(-1)). Rate constants for reaction of the seleno-sugars with HOBr are, similar to 8 times lower than those for HOCl (1.0-1.5 X 10(7) M-1 s(-1)). These values show little variation with differing sugar structures. Reaction with HOSCN is slower (similar to 10(2) M-1 s(-1)) The seleno-sugars decreased the extent of HOCI-mediated oxidation of Met, His, Tip, Lys, and Tyr residues, and 3-chlorotyrosine formation, on both isolated bovine serum albumin and human plasma proteins, at concentrations as low as 50 mu M. These studies demonstrate that novel selenium (and to a lesser extent, sulfur) derivatives of monosaccharides could be potent modulators of peroxidase-mediated damage at sites of acute and chronic inflammation, and in multiple human pathologies.

  DOI：

  10.1021/tx3003593
• 作为产物：
  描述：

  苄基 alpha-D-吡喃葡萄糖苷 在 palladium on activated charcoal 氢气 、 对甲苯磺酸 、 三乙胺 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 20.0 ℃ 、172.37 kPa 条件下， 反应 8.0h， 生成 2,3:4,6-di-O-isopropylidene-D-glucopyranose
  参考文献：
  名称：

  Improved synthesis of 2,3:4,6-di-O-isopropylidene-d-glucopyranose and -d-galactopyranose

  摘要：

  2,3:4,6-Di-O-isopropylidene-D-glucopyranose and -D-galactopyranose acetals are conveniently prepared by hydrogenolysis of benzyl 2,3:4,6-di-O-isopropylidene-beta-D-glucopyranose and -beta-D-galactopyranose in almost quantitative yields in 3 h. This result is in contrast with the sluggish reaction observed (48 h) when the hydrogenolysis was carried out on either anomeric alpha,beta mixtures or on the corresponding a anomers. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(99)00150-0

文献信息

• Dehydrative Thioglycosylation of 1-Hydroxyl Glycosides Catalyzed by In Situ-Generated AlI₃
  作者：Shiue-Shien Weng、Kun-Yi Hsieh、Zih-Jian Zeng

  DOI：10.1002/jccs.201600828

  日期：2017.5

  Thioglycosylation of 1‐hydroxyl glycosides catalyzed by in situ‐generated AlI3 from elemental aluminium and molecular iodine has been developed. This method provides an alternative route to access anomeric thioglycosides without the use of hazard Lewis acidic activators or per‐modified activated thiol sources. The major advantages of this dehydrative procedure are environmental friendly, ease of operation

  已经开发了由元素铝和分子碘原位生成的AlI 3催化的1-羟基糖苷的硫糖基化。该方法提供了另一种途径来使用异头硫醇苷，而无需使用危险的路易斯酸性活化剂或过修饰的活化硫醇源。该脱水步骤的主要优点是环境友好，操作简便，高异头非对映选择性和温和的反应条件。
• Synthetic Strategies Directed Towards 5a-Carbahexopyranoses and Derivatives Based on 6-endo-trig Radical Cyclizations
  作者：Ana M. Gómez、Clara Uriel、Maria D. Company、J. Cristóbal López

  DOI：10.1002/ejoc.201100956

  日期：2011.12

  Several synthetic strategies directed towards 5a-carbahexopyranoses and based on 6-endo-trig radical cyclization of unsaturated carbohydrate derivatives have been devised. Three elements for regiocontrol to optimize the 6-endo/5-exo ratio have been incorporated, and their efficiencies in directing 6-endo cyclizations have been evaluated. These elements – namely: i) the incorporation of a substituent

  已经设计了几种针对 5α-碳己基吡喃糖并基于不饱和碳水化合物衍生物的 6-endo-trig 自由基环化的合成策略。纳入了三个用于区域控制以优化 6-endo / 5-exo 比率的元素，并评估了它们在指导 6-endo 环化方面的效率。这些元素 - 即：i）在 C-5（自由基编号）处引入取代基，ii）使用乙烯基（而不是烷基）基团，以及 iii) 在系统中包含环应变 - 已被证明是有用的组合使用时。它们中的两个同时存在也会导致 6-endo 选择性。在另一个主题上，随后的烯基烷烃臭氧化以提供二醇似乎是基于锡-氧重排，类似于相关乙烯基硅烷的报道，
• Straightforward synthesis of protected 2-hydroxyglycals by chlorination-dehydrochlorination of carbohydrate hemiacetals
  作者：Jan Choutka、Michal Kratochvíl、Jakub Zýka、Radek Pohl、Kamil Parkan

  DOI：10.1016/j.carres.2020.108086

  日期：2020.10

  A straightforward and scalable method for the synthesis of protected 2-hydroxyglycals is described. The approach is based on the chlorination of carbohydrate-derived hemiacetals, followed by an elimination reaction to establish the glycal moiety. 1,2-dehydrochlorination reactions were studied on a range of glycosyl chlorides to provide suitable reaction conditions for this transformation. Benzyl ether

  描述了一种用于合成受保护的 2-hydroxyglycals 的简单且可扩展的方法。该方法基于碳水化合物衍生的半缩醛的氯化，然后是消除反应以建立糖基部分。研究了一系列糖基氯的 1,2- 脱氯化氢反应，以为这种转化提供合适的反应条件。发现苄基醚、异亚丙基和亚苄基保护基团以及糖苷间连接与该协议兼容。所描述的方法操作简单，可以快速制备具有除酯保护基团以外的 2-羟基糖醛，为现有方法提供了可行的替代方案。
• Wittig approach to carbohydrate-derived vinyl sulfides, new substrates for regiocontrolled ring-closure reactions
  作者：Vincent Aucagne、Arnaud Tatibouët、Patrick Rollin

  DOI：10.1016/j.tet.2003.12.040

  日期：2004.2

  Reaction of methyl- and phenylthiomethylidene phosphoranes 1 and 2 with a variety of reducing sugars has been explored. Furano-type carbohydrates afforded with good yields the corresponding open-chain vinyl sulfides, whereas pyrano derivatives produced elimination compounds together with the expected vinyl sulfides, depending on the nature of the protective groups.

  已经研究了甲基和苯基硫代亚甲基膦烷1和2与多种还原糖的反应。呋喃诺型碳水化合物具有良好的收率，可提供相应的开链乙烯基硫化物，而吡喃衍生物则根据保护基团的性质与预期的乙烯基硫化物一起生成消除化合物。
• De‐epimerization of Monosaccharides by Dynamic Kinetic Resolution: Ligand‐Controlled Synthesis of <i>O</i>‐Aryl‐Glycosides through Copper‐Catalyzed Cross‐Coupling
  作者：Tian‐Yang Liu Hou、Yi‐Xian Li、Yue‐Mei Jia、Chu‐Yi Yu

  DOI：10.1002/adsc.202300997

  日期：2024.3.8

  We report a strategy for stereoselective O-aryl-glycoside synthesis by copper-catalyzed cross-coupling of a variety of anomeric sugars and (hetero)aromatic iodides. Stereocontrol of the α/β selectivity can be successfully realized by slight structural modifications of the oxalic diamide ligands. Mechanistic studies indicated a dynamic kinetic resolution (DKR) reaction mechanism controlled by the ligand

  我们报告了一种通过铜催化交叉偶联各种异头糖和（杂）芳香族碘化物来立体选择性 O-芳基糖苷合成的策略。通过草酸二酰胺配体的轻微结构修饰可以成功实现α/β选择性的立体控制。机理研究表明了由配体结构控制的动态动力学拆分（DKR）反应机制。该反应可以在克级进行，并且也已应用于一些天然产物的合成。