3-O-benzyl-1,2-O-isopropylidene-5-O-tosyl-α-D-xylo-furanose | 29581-48-4

• 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: 3-O-benzyl-1,2-O-isopropylidene-5-O-tosyl-α-D-xylo-furanose
• 英文别名: [(3aR,5R,6S,6aR)-2,2-dimethyl-6-phenylmethoxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]methyl 4-methylbenzenesulfonate
• CAS: 29581-48-4
• 化学式: C₂₂H₂₆O₇S
• 分子量: 434.51
• InChiKey: USEPKWIFYVGUCA-PLACYPQZSA-N

物化性质

• 沸点：
  553.6±50.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  88.7
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3-O-benzyl-1,2-O-isopropylidene-5-O-tosyl-α-D-xylo-furanose 在 (4,8-dimethoxynaphthyl)propionic acid 、 一水合肼 作用下， 以 水 、 乙腈 为溶剂， 反应 2.6h， 以68%的产率得到3-O-benzyl-1,2-O-isopropylidene-α-D-xylofuranose
  参考文献：
  名称：

  Extremely mild and selective method for hydrolysis of tosyl esters by photo-sensitized single electron transfer reactions.

  摘要：

  在光敏条件下，用紫外线（>330 纳米）照射对甲苯磺酸酯会发生水解。在肼存在的乙腈水溶液中，1.5-二甲氧基萘和 (4，8-二甲氧基萘基)丙酸对转化有效。该反应成功地应用于糖和核苷的对甲苯磺酸盐的水解。

  DOI：

  10.1248/cpb.38.2977
• 作为产物：
  描述：

  D-古洛糖 在 吡啶 、 sodium tetrahydroborate 、 sodium periodate 、 sodium hydride 、 溶剂黄146 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 生成 3-O-benzyl-1,2-O-isopropylidene-5-O-tosyl-α-D-xylo-furanose
  参考文献：
  名称：

  Titanocene Dihalides and Ferrocenes Bearing a Pendant α-d-Xylofuranos-5-yl or α-d-Ribofuranos-5-yl Moiety. Synthesis, Characterization, and Cytotoxic Activity

  摘要：

  Titanocene dichlorides of general formula [(eta(5)-C5H5)(eta(5)-C5H4R)TiCl2] (where R = 5-deoxy-1,2-di-O-isopropylidene-3-O-benzyl-alpha-D-xylofuranos-5-yl (Xylf) (8a); R = 5-deoxy-1,2-di-O-isopropylidene-3-O-benzyl-alpha-D-ribofuranos-5-yl (Ribf) (8b)) and [(eta(5)-C5H4R)(2)TiCl2] (R = Xylf (9a); R = Ribf (9b)) were prepared by reaction of the corresponding lithium cyclopentadienides 7a,b with an equimolar amount of [(eta(5)-C5H5)TiCl3] or a 0.5 mol amount of [TiCl4(THF)(2)]. Titanocene difluorides of the general formula [(eta(5)-C5H4R1)(eta(5)-C5H4R2)TiF2] (R-1 = H and R-2 = Ribf (10); R-1 = R-2 = Xylf (11a); R-1 = R-2 = Ribf (11b)) were obtained by fluorination of the corresponding titanocene dichlorides 8b and 9 with the fluorinating agent {2-(CH2NMe2)C6H4-kappa C,N}(n-Bu)(2)SnF in high yields. Alternatively, complexes 11 were prepared in a straightforward way by direct reaction of [TiF4(THF)(2)] with 2 equiv of the corresponding lithium cyclopentadienide 7a,b. Ferrocene complexes [(eta(5)-C5H4R)(2)Fe] (R = Xylf (12a); R = Ribf (12b)) were synthesized by metathesis of 2 equiv of lithium cyclopentadienide 7a,b and 1 equiv of anhydrous FeCl2. Deprotection of the benzyl group in ferrocenes 12 proceeded cleanly by a catalytic hydrogenation on Pd/C and afforded the ferrocene diols [(eta(5)-C3H4R)(2)Fe] (R = 5-deoxy-1,2-di-O-isopropylidene-alpha-D-xylofuranos-5-yl (Xylf-OH) (14a); R = 5-deoxy-1,2-di-O-isopropylidene-alpha-D-ribofuranos-5-yl (Ribf-OH) (14b)). A scaled up benzyl deprotection with Et3SiH as a hydrogen source led to the replacement of only one benzyl group, which gave the ferrocene alcohol [(eta(5)-C5H4R1)(eta(5)-C5H4R2)Fe] (R-1 = Xylf and R-2 = Xylf-OH (13)). The prepared complexes were characterized by elemental analysis, melting point determination, NMR, IR, and ESI-MS, and the molecular structure of 9b was determined by X-ray diffraction analysis. The cytotoxic activity of complexes 8-14 against A2780 and A2780cis cancer cells was evaluated by MTT tests. Titanocene difluorides 10 and 11 and ferrocene diol 14a showed cytotoxicity against A2780 cells in the medium to low micromolar range, while the most active species, 11b, displayed about 40% higher cytotoxicity against A2780cis in comparison to a cisplatin standard.

  DOI：

  10.1021/om500200r

文献信息

• First stereoselective total synthesis of stagonolide G
  作者：P. Srihari、B. Kumaraswamy、Dinesh C. Bhunia、J.S. Yadav

  DOI：10.1016/j.tetlet.2010.03.102

  日期：2010.5

  First stereoselective total synthesis of nonenolide stagonolide G involving a convergent strategy is described. The key reactions include Keck allylation and Grubbs ring closing metathesis reaction.

  描述了涉及收敛策略的壬烯醇内酯Stagonolide G的第一个立体选择性全合成。关键反应包括Keck烯丙基化反应和Grubbs闭环易位反应。
• Synthesis of Triazole‐Containing Furanosyl Nucleoside Analogues and Their Phosphate, Phosphoramidate or Phoshonate Derivatives as Potential Sugar Diphosphate or Nucleotide Mimetics
  作者：Andreia Fortuna、Paulo J. Costa、M. Fátima M. Piedade、M. Conceição Oliveira、Nuno M. Xavier

  DOI：10.1002/cplu.202000424

  日期：2020.8

  The synthesis of stable and potentially bioactive xylofuranosyl nucleoside analogues and potential sugar diphosphate or nucleotide mimetics comprising a 1,2,3‐triazole moiety is reported. 3′‐O‐Methyl‐branched N‐benzyltriazole isonucleosides were accessed in 5–7 steps and 42–54 % overall yields using a Cu(I)‐catalyzed cycloaddition of 3‐O‐propargyl‐1,2‐O‐isopropylidene‐α‐D‐xylofuranose with benzyl azide

  据报道合成了稳定且具有潜在生物活性的木呋喃糖基核苷类似物和潜在的糖二磷酸或包含1,2,3-三唑部分的核苷酸模拟物。3'- ø -甲基支链Ñ -benzyltriazole在异核苷掺入5-7的步骤和使用Cu（I）的3-环加成催化的42-54％的总产率被访问ö -propargyl -1,2- ö异亚丙基α-D-木呋喃糖和叠氮化苄是关键步骤。相关isonucleotides通过获得5- Ö的丙酮保护3- -phosphorylation ö -propargyl呋喃木糖和进一步的“点击”环加成或通过5-叠氮的施陶丁格-亚磷酸酯反应Ñ-苄基三唑异核苷。羟基，氨基或溴甲基三唑5'-异核苷是通过5-叠氮基3- O-苄基/十二烷基木呋喃糖与炔丙醇，炔丙基胺或炔丙基溴的热环加成反应合成的。当使用炔丙醇时，可获得较高的收率（82–85％），而炔丙基溴可获得较高的1,4-区域选择性。进一步的O / N磷酸化
• Synthesis of Benz-Fused Azoles via C-Heteroatom Coupling Reactions Catalyzed by Cu(I) in the Presence of Glycosyltriazole Ligands
  作者：Nidhi Mishra、Anoop S. Singh、Anand K. Agrahari、Sumit K. Singh、Mala Singh、Vinod K. Tiwari

  DOI：10.1021/acscombsci.9b00004

  日期：2019.5.13

  and contain multiple metal-binding units that may assist in metal-mediated catalysis. Azide derivatives of d-glucose have been converted to their respective aryltriazoles and screened as ligands for the synthesis of 2-substituted benz-fused azoles and benzimidazoquinazolinones by Cu-catalyzed intramolecular Ullmann type C-heteroatom coupling. Good to excellent yields for a variety of benz-fused heterocyles

  糖基三唑可以方便地获得，并且包含多个金属结合单元，可以协助金属介导的催化作用。d-葡萄糖的叠氮化物衍生物已被转化为它们各自的芳基三唑，并被筛选为通过铜催化的分子内Ullmann型C-杂原子偶联合成2-取代的苯并稠合的唑和苯并咪唑并喹唑啉酮的配体。对于这种容易获得的催化体系，获得了多种苯并稠合杂环的良好或优异的产率。
• Highly Diastereoselective Route to α-Glucosidase Inhibitors, Neosalacinol and Neoponkoranol
  作者：Genzoh Tanabe、Youya Matsuda、Misato Oka、Yousuke Kunikata、Nozomi Tsutsui、Weija Xie、Gorre Balakishan、Mumen F. A. Amer、Shinsuke Marumoto、Osamu Muraoka

  DOI：10.1021/acs.joc.5b02894

  日期：2016.4.15

  A facile and highly diastereoselective route to potent natural α-glucosidase inhibitors, i.e., neosalacinol (4) and neoponkoranol (6), isolated from the traditional Ayurvedic medicine “Salacia” was developed by intramolecular cyclization of appropriately substituted sulfides (9 and 12).

  通过分子内环化适当取代的硫化物（9和12），开发了一种从有效的天然α-葡萄糖苷酶抑制剂（即新来塞那诺（4）和新ponkoranol（6））分离而来的简便且高度非对映选择性的途径，该抑制剂从传统的阿育吠陀药物“ Salacia ”中分离出来。
• 1-Aza-sugars from d -glucose. Preparation of 1-deoxy-5-dehydroxymethyl-nojirimycin, its analogues and evaluation of glycosidase inhibitory activity
  作者：Nitin T Patil、Sheeja John、Sushma G Sabharwal、Dilip D Dhavale

  DOI：10.1016/s0968-0896(02)00073-1

  日期：2002.7

  D-glucose derived pentodialdoses 11a-c on reduction followed by tosylation, azide displacement, hydrogenation and protection with -Cbz group gave N-Cbz protected compounds 14a-c, respectively, which on removal of 1,2-acetonide functionality and hydrogenation afforded corresponding 1-aza-sugars 3, 9 and 10 in good overall yields. The glycosidase inhibition activity of these 1-aza-sugars was tested with

  D-葡萄糖衍生的戊二醛糖11a-c还原，然后进行甲苯磺酸化，叠氮化物置换，氢化和用-Cbz基团保护，分别得到N-Cbz保护的化合物14a-c，该化合物在除去1,2-丙酮化物官能团和氢化后提供相应的1-氮杂糖3、9和10的总产量良好。用甜杏仁作为不同糖苷酶的丰富来源测试了这些1-氮杂糖的糖苷酶抑制活性。