2,3:4,6-di-O-isopropylidene-D-mannopyranose | 357604-61-6

• 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-mannopyranose
• 英文别名: (1R,2S,6S,9R)-4,4,12,12-tetramethyl-3,5,8,11,13-pentaoxatricyclo[7.4.0.02,6]tridecan-7-ol
• CAS: 357604-61-6
• 化学式: C₁₂H₂₀O₆
• 分子量: 260.287
• InChiKey: QIFUEBARKWFBGQ-NTUKYRGVSA-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-mannopyranose 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成 2,3,5,6-di-isopropyIidene-1,4-dihydroxy-D-mannitol
  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：

  allyl 2,3:4,6-di-O-isopropylidene-α-D-mannopyranoside 在 potassium tert-butylate 、 mercury(II) diacetate 作用下， 以 二甲基亚砜 、 四氢呋喃 、 水 为溶剂， 反应 1.33h， 以97%的产率得到2,3:4,6-di-O-isopropylidene-D-mannopyranose
  参考文献：
  名称：

  Synthesis of β-d-Galp-(1→4)-α-d-Manp methanephosphonate, a substrate analogue for the elongating α-d-mannosyl phosphate transferase in the Leishmania

  摘要：

  An isosteric C-glycoside phosphono analogue of dec-9-enyl beta -D-galactopyranosyl-(1 -->4)-alpha -D-mannopyranosyl phosphate was synthesised and showed high biological activity in the Leishmania MPT assay. A one-step Horner-Emmons/Michael reaction was developed for the stereoselective preparation of cc-D-mannosyl methanephosphonate derivatives. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00961-3

文献信息

• Oxidative Cyclizations, the Synthesis of Aryl-Substituted C-Glycosides, and the Role of the Second Electron Transfer Step
  作者：Jake A. Smith、Kevin D. Moeller

  DOI：10.1021/ol402826z

  日期：2013.11.15

  Anodic oxidation reactions have been used to synthesize aryl- and biaryl-substituted C-glycosides. The reactions take advantage of the tendency for alcohol nucleophiles to trap nonpolar radical cations. The addition of the alcohol to the radical cation appears to be reversible, and the success of the cyclizations is dependent on the ease with which the resulting benzylic radical is oxidized.

  阳极氧化反应已用于合成芳基和联芳基取代的C-糖苷。该反应利用了醇亲核试剂捕获非极性自由基阳离子的趋势。醇加到自由基阳离子上似乎是可逆的，并且环化的成功取决于所得苄基被氧化的难易程度。
• Reaction of cyclic ketals with ceric ammonium nitrate in acetonitrile/water
  作者：Emiliano Manzo、Gaspare Barone、Emiliano Bedini、Alfonso Iadonisi、Lorenzo Mangoni、Michelangelo Parrilli

  DOI：10.1016/s0040-4020(01)01006-7

  日期：2002.1

  performing the hydrolysis of cyclic acetals and ketals under basic or mildly alkaline conditions by ceric ammonium nitrate (CAN) in MeCN/H2O or in 10% aq. methanol is rejected. However a role for Ce(IV) as Lewis acid is evidenced at pH 4.4. Under these conditions, which allow hydrolysis of cyclic ketals leaving glycosidic bonds unaltered, a selectivity of ketal cleavage due to steric hindrance is also

  在碱性或弱碱性条件下，通过硝酸铈铵（CAN）在MeCN / H 2 O或10％水溶液中进行环状缩醛和缩酮水解的可能性。甲醇被拒绝。然而，在pH 4.4下证明了Ce（IV）作为路易斯酸的作用。在这些条件下，允许环缩酮水解而糖苷键保持不变，还可以观察到由于空间位阻而引起的缩酮切割的选择性。当丙酮/水代替MeCN / H 2 O作为溶剂时，可获得相似的收率。
• Synthesis of zwitterionic selenonium and sulfonium sulfates from <scp>D</scp>-mannose as potential glycosidase inhibitors
  作者：Hui Liu、B Mario Pinto

  DOI：10.1139/v06-027

  日期：2006.4.1

  studies with different glycosidase enzymes. The syntheses involved the reaction of isopropylidene-protected 1,4-thio- and 1,4-seleno-D-talitols and 1,5-thio- and 1,5-seleno-L-gulitols, derived from D-mannose, with a benzylidene- and isopropylidene-protected 1,3-cyclic sulfate, also derived from D-mannose. Deprotection of the products afforded the novel selenonium and sulfonium sulfates composed of heterocyclic

  合成了四种天然糖苷酶抑制剂salacinol 的链延长类似物，用于不同糖苷酶的结构活性研究。合成涉及异丙叉保护的 1,4-硫代-和 1,4-硒-D-塔糖醇与衍生自 D-甘露糖的 1,5-硫代-和 1,5-硒-L-gulitols 与亚苄基和异亚丙基保护的 1,3- 环硫酸盐，也衍生自 D-甘露糖。产物的脱保护提供了由杂环五元和六元环核心结构组成的新型硒和锍硫酸盐，具有多羟基化的六碳原子无环链。 关键词：糖苷酶抑制剂，两性离子硒和锍硫酸盐，环硫酸盐
• Sulfuric acid immobilized on silica: an efficient reusable catalyst for the synthesis of O-isopropylidene sugar derivatives
  作者：Vishal Kumar Rajput、Balaram Mukhopadhyay

  DOI：10.1016/j.tetlet.2006.06.050

  日期：2006.8

  Sulfuric acid immobilized on silica proved to be an efficient catalyst for the synthesis of O-isopropylidene sugar derivatives from reducing sugars. The method is very simple and economic for large-scale synthesis in which the catalyst is recovered and reused several times. Reactions with d-glucose, d-galactose, d-mannose, l-rhamnose, l-arabinose, d-xylose and l-sorbose led to the formation of the corresponding

  固定在二氧化硅上的硫酸被证明是从还原糖合成O-异亚丙基糖衍生物的有效催化剂。该方法对于大规模合成非常简单且经济，其中催化剂被回收并重复使用多次。与d-葡萄糖，d-半乳糖，d-甘露糖，l-鼠李糖，l-阿拉伯糖，d-木糖和l-山梨糖的反应导致形成相应的热力学稳定的二-O-和/或单-O-异亚丙基衍生品，收益率高至优。
• A Stereodivergent Approach to 5a-Carba-α-D-gluco-, -α-D-galacto and -β-L-gulopyranose Pentaacetates fromD-Mannose, Based on 6-exo-dig Radical Cyclization and Barton−McCombie Radical Deoxygenation
  作者：Ana M. Gómez、Eduardo Moreno、Serafín Valverde、J. Cristóbal López

  DOI：10.1002/ejoc.200300339

  日期：2004.4

  The three carbasugars, 5a-carba-α-D-gluco-, -α-D-galacto and -β-L-gulopyranose pentaacetates 42, 35 and 28 respectively, have been prepared in a stereodivergent manner from D-mannose. Alkynyl derivatives of 2,3:4,6-di-O-isopropylidene-D-mannopyranose, which are homologated at C-1 by reaction with trimethylsilylacetylide, undergo a 6-exo-dig radical cyclization, from a radical located at C-5, to yield

  三种碳水化合物，5a-carba-α-D-葡萄糖-、-α-D-半乳糖和-β-L-吡喃葡萄糖五乙酸酯分别为 42、35 和 28，已从 D-甘露糖以立体发散方式制备。2,3:4,6-二-O-异亚丙基-D-吡喃甘露糖的炔基衍生物，通过与三甲基甲硅烷基乙炔反应在C-1处同系化，从位于C-的自由基经历6-exo-dig自由基环化5，得到高度官能化的外-亚甲基环己烷的混合物。后者中环外双键的臭氧分解产生环己酮，通过羰基部分的立体选择性还原，然后在 C-4 或 C-5a 位（母体碳水化合物编号）进行位点选择性脱氧，得到标题碳糖。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)