1,6-anhydro-2,4-di-O-p-tolylsulfonyl-β-D-ribo-hexopyranos-3-ulose | 20325-18-2

• 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: 1,6-anhydro-2,4-di-O-p-tolylsulfonyl-β-D-ribo-hexopyranos-3-ulose
• 英文别名: 1,6-anhydro-2,4-di-O-tosyl-β-D-ribo-hexopyranos-3-ulose；[(1R,2R,4S,5R)-4-(4-methylphenyl)sulfonyloxy-3-oxo-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate
• CAS: 20325-18-2
• 化学式: C₂₀H₂₀O₉S₂
• 分子量: 468.505
• InChiKey: GYMOKJFTGMJNGT-VBSBHUPXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  139
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1,6-anhydro-2,4-di-O-p-tolylsulfonyl-β-D-ribo-hexopyranos-3-ulose 在 盐酸 、 ammonium acetate 、 锌 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 20.0h， 以85%的产率得到1,6-anhydro-2,4-dideoxy-β-D-glycero-hexopyranos-3-ulose
  参考文献：
  名称：

  Open Chain Chiral Macrolide Building Blocks by Opening of Deoxygenated 1,6-Anhydrosugars with 1,3-Propanedithiol

  摘要：

  Chiral building blocks for macrolides and related natural products are obtained from 1,6-anhydrosugars by conversion of the bicyclic acetals 2 or 12 into the open chain chiral 1,3-dithianes 6 and 13. Branched precursors can be obtained by opening of the Cerny epoxide 1 with the 1,3-dithiane anion to yield 7, followed by ring opening with 1,3-propanedithiol to the bis-1,3-dithiane 8.

  DOI：

  10.1080/07328300802691851
• 作为产物：
  描述：

  1,6-脱水-β-D-葡萄糖 在 吡啶 、 ruthenium trichloride 、 sodium bromate 作用下， 以 水 、 溶剂黄146 、 乙腈 为溶剂， 反应 15.5h， 生成 1,6-anhydro-2,4-di-O-p-tolylsulfonyl-β-D-ribo-hexopyranos-3-ulose
  参考文献：
  名称：

  Practical Synthesis of 1,6-Anhydro-2,4-dideoxy-β-d-glycero- hexopyranos-3-ulose from Levoglucosan

  摘要：

  DOI：

  10.1021/jo991719w

文献信息

• Synthesis of 1,6-Anhydro-β-D-hexopyranoses Fused to the Piperidine Ring
  作者：Tomáš Trtek、Miloslav Černý、Miloš Buděšínský、Tomáš Trnka、Ivana Císařová

  DOI：10.1135/cccc20051429

  日期：——

  Two piperidine derivatives (6 and 17) containing fused 1,6-anhydro-β-D-hexopyranose moiety were prepared from 1,6-anhydro-β-D-glucopyranose (1). The first synthetic route led via the known 1,6:2,3-dianhydro-4-deoxy-4-(3-hydroxypropyl)-β-D-mannopyranose (2) obtained in four steps from 1. Its hydroxyl group was converted into amino group via tosylate and azide. The corresponding amino epoxide 5 readily rearranged into 3-amino-1,6-anhydro-3,4-dideoxy-3-N,4-C-(propane-1,3-diyl)-β-D-altropyranose (6). The second route used the known 1,6-anhydro-2,4-di-O-tosyl-β-D-ribo-hexopyranos-3-ulose (9) as an intermediate. Addition of allylmagnesium chloride to ketose 9 afforded 3-C-allyl-1,6-anhydro-2,4-di-O-tosyl-β-D-allopyranose (10). Hydroboration of its double bond followed by transformation of the resulting primary hydroxyl group into tosylamido group gave tritosyl derivative 15. Intramolecular replacement of the tosyloxy group in position 4 by tosylamido group gave tosylated piperidine derivative 16. Detosylation of 16 afforded the target 4-amino-1,6-anhydro-3,4-dideoxy-3-C,4-N-(propane-1,3-diyl)-β-D-gulopyranose (17).

  制备了两种含有融合的1,6-去水β-D-己糖苷基的哌啶衍生物（6和17），它们是由1,6-去水β-D-葡萄糖苷（1）制备而成。第一种合成路线通过已知的1,6:2,3-二去水-4-去氧-4-(3-羟基丙基)-β-D-甘露糖苷（2）制备，该化合物经过四步反应从1得到。其羟基经过tosylate和azide转化为氨基。相应的氨基环氧化合物5很容易重排成3-氨基-1,6-去水-3,4-二去氧-3-N,4-C-(丙烷-1,3-二基)-β-D-阿尔卓糖苷（6）。第二种路线使用已知的1,6-去水-2,4-二-O-tosyl-β-D-核-己糖苷-3-酮（9）作为中间体。将烯丙基氯化镁加入酮糖9中，得到3-C-烯丙基-1,6-去水-2,4-二-O-tosyl-β-D-阿洛糖苷（10）。其双键的氢化后，将产生的一级羟基转化为tosylamido基团，得到tritosyl衍生物15。将位置4的tosyloxy基团通过分子内置换为tosylamido基团，得到tosyl化的哌啶衍生物16。将16去除tosyl基团，得到目标化合物4-氨基-1,6-去水-3,4-二去氧-3-C,4-N-(丙烷-1,3-二基)-β-D-古罗糖苷（17）。
• Practical Synthesis of 1,6-Anhydro-2,4-dideoxy-β-<scp>d</scp>-glycero- hexopyranos-3-ulose from Levoglucosan
  作者：Kevin M. Belyk、William R. Leonard,、Dean R. Bender、David L. Hughes

  DOI：10.1021/jo991719w

  日期：2000.4.1
• Open Chain Chiral Macrolide Building Blocks by Opening of Deoxygenated 1,6-Anhydrosugars with 1,3-Propanedithiol
  作者：Karsten Krohn、Ishtiaq Ahmed、Dietmar Gehle、Mohammed Al Sahli

  DOI：10.1080/07328300802691851

  日期：2009.2.27

  Chiral building blocks for macrolides and related natural products are obtained from 1,6-anhydrosugars by conversion of the bicyclic acetals 2 or 12 into the open chain chiral 1,3-dithianes 6 and 13. Branched precursors can be obtained by opening of the Cerny epoxide 1 with the 1,3-dithiane anion to yield 7, followed by ring opening with 1,3-propanedithiol to the bis-1,3-dithiane 8.