1,2:3,4-di-O-isopropylidene-6-O-methylsulphonyl-α-D-galactopyranose | 4148-55-4

• 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: 1,2:3,4-di-O-isopropylidene-6-O-methylsulphonyl-α-D-galactopyranose
• 英文别名: 6-O-Mesyl-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside；1,2:3,4-Di-O-isopropyliden-6-O-mesyl-α-D-galactopyranose；(-)-1,2:3,4-di-O-isopropylidene-6-O-methylsulfonyl-α-D-galactopyranose；1,2:3,4-di-O-isopropylidene-6-O-methanesulfonyl-α-D-galactopyranose；O¹,O²;O³,O⁴-diisopropylidene-O⁶-methanesulfonyl-α-D-galactopyranose；((3aR,5R,5aS,8aS,8bR)-2,2,7,7-tetramethyltetrahydro-5Hbis([1,3]dioxolo)[4,5-b:4',5'-d]pyran-5-yl)methyl methanesulfonate；1,2:3,4-di-O-isopropylidene-6-methanesulfonate-6-deoxy-α-D-galactopyranose；1.2:3.4-Di-O-isopropyliden-α-D-galactose-6-methansulfonat；6-O-Methansulfonyl-1.2:3.4-di-O-isopropyliden-D-galactose；O¹,O²;O³,O⁴-Diisopropyliden-O⁶-methansulfonyl-α-D-galactopyranose；1,2:3,4-Diisopropylidene-alpha-d-galactopyranose-6-mesyl ester；[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methyl methanesulfonate
• CAS: 4148-55-4
• 化学式: C₁₃H₂₂O₈S
• 分子量: 338.379
• InChiKey: JNTTVQLLUZKLPW-ZKKRXERASA-N

物化性质

• 熔点：
  118 °C(Solv: isopropyl ether (108-20-3))
• 沸点：
  448.8±40.0 °C(Predicted)
• 密度：
  1.244±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  97.9
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,2:3,4-di-O-isopropylidene-6-O-methylsulphonyl-α-D-galactopyranose 在 丙酮 、 sodium iodide 作用下， 生成 6-脱氧-6-碘-1,2:3,4-二-o-异亚丙基-α-d-半乳糖吡喃糖苷
  参考文献：
  名称：

  Foster et al., Journal of the Chemical Society, 1949, p. 2542,2545

  摘要：

  DOI：
• 作为产物：
  描述：

  alpha-D-半乳糖 在 copper(ll) sulfate pentahydrate 、 三乙胺 作用下， 以 二氯甲烷 、 硫酸 为溶剂， 反应 24.5h， 生成 1,2:3,4-di-O-isopropylidene-6-O-methylsulphonyl-α-D-galactopyranose
  参考文献：
  名称：

  Synthesis and antiproliferative activity of 8-hydroxyquinoline derivatives containing a 1,2,3-triazole moiety

  摘要：

  Twelve novel 8-hydroxyquinoline derivatives were synthesized with good yields by performing copper-catalyzed Huisgen 1,3-dipolar cycloaddition ("click" reaction) between an 8-O-alkylated-quinoline containing a terminal alkyne and various aromatic or protected sugar azides. These compounds were evaluated in vitro for their antiproliferative activity on various cancer cell types. Protected sugar derivative 16 was the most active compound in the series, exhibiting potent antiproliferative activity and high selectivity toward ovarian cancer cells (OVCAR-03, GI50 < 0.25 μg mL(-1)); this derivative was more active than the reference drug doxorubicin (OVCAR-03, GI50 = 0.43 μg mL(-1)). In structure-activity relationship (SAR) studies, the physico-chemical parameters of the compounds were evaluated and docking calculations were performed for the α-glucosidase active site to predict the possible mechanism of action of this series of compounds.

  DOI：

  10.1016/j.ejmech.2014.07.061

文献信息

• Synthesis of amino-substituted hexo- and heptopyranoses from d-galactose
  作者：Benedikt Streicher、Bernhard Wünsch

  DOI：10.1016/s0008-6215(03)00382-3

  日期：2003.10

  After condensation of D-galactose with two equivalents of acetone, the last free hydroxy group was transformed into an acylated amino group by Swern oxidation, oxime formation, LiAlH4 reduction and acylation. The intermediate aldehyde was homologated with the Wittig reagent, (methoxymethyl)triphenylphosphonium chloride, to afford, after careful hydrolysis, a homologous heptodialdo-1,5-pyranose. Condensation

  D-半乳糖与两当量的丙酮缩合后，最后的游离羟基通过Swern氧化，肟形成，LiAlH4还原和酰化作用转变为酰化氨基。用Wittig试剂氯化（甲氧基甲基）三苯基phosph将中间体醛均化，在仔细水解后得到同源的庚二醛-1，5-吡喃糖。醛与羟胺的缩合和随后的LiAlH4还原提供了一个双-O，O-异亚丙基保护的7-氨基-6,7-二脱氧半乳糖庚基吡喃糖，其被各种羧酸衍生物酰化。通过仔细的水解或醇解作用裂解异亚丙基保护基团，得到6-酰基氨基-6-脱氧半乳糖吡喃糖和7-酰基氨基-6,7-二脱氧半乳糖庚基-吡喃糖。
• SYNTHESIS OF 6-AMINO-6-DEOXY-2,3,4,5- TETRA-O-METHYL-D-GALACTONIC ACID, A KEY PRECURSOR OF A STEREOREGULAR POLYAMIDE1
  作者：Carmen Zaliz、Oscar Varela

  DOI：10.1081/car-100108283

  日期：——

  α-pyranoside (6). Methylation of the free hydroxyl groups of 5 and 6 gave the respective per-O-methyl derivatives 7 and 8. In order to maintain the size of the sugar ring during the sequence, compound 8 was alternatively prepared from 9, by acetylation, substitution by azide and per-O-methylation. Hydrolysis of the glycoside followed by oxidation and further 5-O-methylation afforded the 6-azido-6-deoxy carboxylic

  标题化合物（17）是通过两个替代序列合成的，从D-半乳糖二丙酮化物（1）和甲基6 - O-甲苯磺酰基-α- D-吡喃半乳糖苷（9）开始。化合物1被转化为6-溴-6-脱氧衍生物2或被甲磺化为3。用叠氮化钠对2和3中的离去基团进行亲核取代，生成6-叠氮基6-脱氧衍生物4，在酸性条件下用甲醇处理后，得到相应的甲基β-呋喃糖苷（5）和α-吡喃糖苷（6）。的游离羟基基团的甲基化5和6，得到相应的per- ø -甲基衍生物7和8。为了在序列中维持糖环的大小，可替代地由9通过乙酰化，叠氮化物取代和过-O-甲基化制备化合物8。糖苷水解，然后氧化并进一步5- O-甲基化，得到6-叠氮基-6-脱氧羧酸16，其通过叠氮化物官能团的氢解转化为17（从9得到的总产率为38％）。
• Molybdenum oxide-mediated facile aliphatic nucleophilic fluorination
  作者：Madhukar S. Said、Lina Khandare、Sandip S. Shinde

  DOI：10.1016/j.tetlet.2016.11.099

  日期：2017.1

  A facile aliphatic nucleophilic fluorination with cesium fluoride in the presence of molybdenum oxide as a catalyst has been demonstrated. Reactivity of molybdenum oxide in nanocrystal form was found to be chemoselective in the presence of water. Furthermore, the reaction is highly specific with alkyl sulfonate substrates.

  已经证明在氧化钼存在下用氟化铯容易地进行脂族亲核氟化。发现在水存在下，纳米晶形式的氧化钼的反应性是化学选择性的。此外，该反应对于烷基磺酸盐底物是高度特异性的。
• Synthesis of seleno-carbohydrates derived from d-galactose
  作者：Hugo C. Braga、Ana D. Wouters、Felipe B. Zerillo、Diogo S. Lüdtke

  DOI：10.1016/j.carres.2010.08.019

  日期：2010.11

  The synthesis of seleno-galactopyranosides in a short and efficient manner is described, starting from the parent carbohydrate d-galactose. The approach described allows the synthesis of small libraries of compounds with a number of structural variations at the group attached to selenium. Compounds with aryl, propargyl, allyl, acyl, and alkyl substituents are described.

  从母体碳水化合物d-半乳糖开始，以简短而有效的方式描述了硒代-半乳糖吡喃糖苷的合成。所描述的方法允许合成小的化合物库，该化合物库在与硒连接的基团上具有许多结构变异。描述了具有芳基，炔丙基，烯丙基，酰基和烷基取代基的化合物。
• Reaktionen mit und in wasserfreiem Fluorwasserstoft 7.¹Von Isopropylidenzuckern zu acylierten Pyranosyl- oder Furanosylfluoriden in einem Schritt
  作者：Ralf Miethchen、Torsten Gabriel、Gundula Kolp

  DOI：10.1055/s-1991-26601

  日期：——

  Reactions with and in Anhydrous Hydrogen Fluoride 7.1 From Isopropylidene Sugars to Acylated Pyranosyl and Furanosyl Fluorides in One Step A convenient one-pot transformation of the 6-O-substituted 1,2:3,4-di-O-isopropylidene-α-D-galactopyranoses 1a-g and the 3-O-substituted 1,2:5,6-di-O-isopropylidene-α-D-glucofuranoses 5a-c is described to form the corresponding 6-O-substituted 2,3, 4-tri-O-acyl-α-D-galactopyranosyl fluorides 2a-f, 3e, 3g and 3-O-substituted 2,5,6-tri-O-acetyl-α/β-D-glucofuranosyl fluorides 6a-c, respectively. This short way of synthesis is possible by use of the new homogeneous reagent/catalyst/solvent combination composed of anhydrous hydrogen fluoride/nitromethane/carboxylic acid anhydride (2: 5:1-1.5). A ring contraction or extension is not found; in addition the functional groups are regiostable in 6-position of 2a-f, 3e, 3g and in 3-position of 6a-c, respectively.

  与无水氟化氢的反应 7.1 从异丙基糖到酰化吡喃糖和呋喃糖氟化物的一步法 一种便捷的单锅转化方法被描述，用于将6-O-取代的1,2:3,4-二-O-异丙基化α-D-半乳糖吡喃糖（1a-g）和3-O-取代的1,2:5,6-二-O-异丙基化α-D-葡萄糖呋喃糖（5a-c）转化为相应的6-O-取代的2,3,4-三-O-酰化α-D-半乳糖吡喃糖氟化物（2a-f, 3e, 3g）以及3-O-取代的2,5,6-三-O-乙酰化α/β-D-葡萄糖呋喃糖氟化物（6a-c）。这种简短的合成方法得益于新的均相试剂/催化剂/溶剂组合，包含无水氟化氢/硝基甲烷/羧酸酐（2:5:1-1.5）。未发现环收缩或扩展；此外，功能基团在2a-f, 3e, 3g的6位和6a-c的3位均表现出区域稳定性。