2-O-dimethylvinylsilyl ether of 3,4,6-tri-O-benzyl-1-phenylselenyl-β-D-glucose | 240483-01-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-O-dimethylvinylsilyl ether of 3,4,6-tri-O-benzyl-1-phenylselenyl-β-D-glucose
• 英文别名: phenyl 2-O-dimethylvinylsilyl-3,4,6-tri-O-benzyl-1-seleno-β-D-glucopyranoside；[(2S,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-phenylselanyloxan-3-yl]oxy-ethenyl-dimethylsilane
• CAS: 240483-01-6
• 化学式: C₃₇H₄₂O₅SeSi
• 分子量: 673.783
• InChiKey: MXNLGQKBNBWEIG-MANRWTMFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.44
• 重原子数：
  44
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-O-dimethylvinylsilyl ether of 3,4,6-tri-O-benzyl-1-phenylselenyl-β-D-glucose 在 偶氮二异丁腈 、 三正丁基氢锡 、 potassium fluoride 、 双氧水 、 potassium hydrogencarbonate 作用下， 以 氯苯 、 四氢呋喃 、 甲醇 为溶剂， 反应 16.0h， 生成 (2R,3R,4S)-4-benzyloxy-6-benzyloxymethyl-3,4-dihydro-3-hydroxy-2-[(1S)-1-hydroxyethyl]-2H-pyran 、 (2R,3S,4R,5S,6S)-4,5-dibenzyloxy-6-benzyloxymethyl-3-hydroxy-2-(2-hydroxyethyl)tetrahydropyran
  参考文献：
  名称：

  Synthesis of 3,7-Anhydro-d-glycero-d-ido-octitol 1,5,6-Trisphosphate as an IP₃ Receptor Ligand Using a Radical Cyclization Reaction with a Vinylsilyl Tether as the Key Step. Conformational Restriction Strategy Using Steric Repulsion between Adjacent Bulky Protecting Groups on a Pyranose Ring

  摘要：

  3,7-Anhydro-D-glycero-D-ido-octitol 1,5,6-trisphosphate (5) was designed as a novel IP3-receptor ligand having a C-glycosidic structure and was synthesized via a radical cyclization reaction with a temporary connecting vinylsilyl tether as the key step. The phenyl 2-O-dimethylvinylsilyl-3,4,6-tri-O-benzyl-1-seleno-beta-D-glucopyranoside (7), in the usual C-4(1)-conformation, was successively treated with Bu3SnH/AIBN and under Tamao oxidation conditions to give a mixture of five C-glycosidic products, On the other hand, similar successive treatment of the corresponding 3,4-di-O-TBS-protected substrates 13 and 24, which were in an unusual C-1(4)-conformaion due to the steric repulsion between the bulky silyl protecting groups, gave the desired 1 alpha-C-glycosides 18 and 25, respectively, as the major products. Thus, the course of the radical cyclization was effectively controlled by a change in the conformation of the pyranose ring into a C-1(4)-form due to steric repulsion between the adjacent bulky TBS-protecting groups at the 3- and 4-hydroxyl groups. From 25, the target 5 was synthesized via phosphorylation of the hydroxyls by the phosphoramidite method. The C-glycoside trisphosphate 5 has significant binding affinity for IP3 receptor of calf cerebella.

  DOI：

  10.1021/jo0002339
• 作为产物：
  描述：

  二甲基乙烯基氯硅烷 、 phenyl 3,4,6-tri-O-benzyl-1-seleno-β-D-glucopyranoside 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 甲苯 为溶剂， 生成 2-O-dimethylvinylsilyl ether of 3,4,6-tri-O-benzyl-1-phenylselenyl-β-D-glucose
  参考文献：
  名称：

  通过与乙烯基甲硅烷基系链的自由基环化反应合成C-糖苷。通过相邻的大分子保护基之间的空间排斥而改变吡喃糖环的构型来控制反应过程

  摘要：

  开发了一种立体选择性的方法，该方法通过乙烯基乙烯基作为临时连接链的自由基环化反应，分别在d-葡萄糖和d-甘露糖的1α-和1β-位引入C2-单元。通过由于相邻的大体积TBS-保护基团之间的空间排斥而使吡喃糖环的构型改变为1 C 4-形式，有效地促进了d-葡萄糖底物的自由基环化。

  DOI：

  10.1016/s0040-4039(99)01026-6