(2R,3R,4R)-3,4-bis(tert-butyldimethylsiloxy)-3,4-dihydro-2-(triphenylmethoxymethyl)-2H-pyran | 288584-98-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: (2R,3R,4R)-3,4-bis(tert-butyldimethylsiloxy)-3,4-dihydro-2-(triphenylmethoxymethyl)-2H-pyran
• 英文别名: tert-butyl-[[(2R,3R,4R)-3-[tert-butyl(dimethyl)silyl]oxy-2-(trityloxymethyl)-3,4-dihydro-2H-pyran-4-yl]oxy]-dimethylsilane
• CAS: 288584-98-5
• 化学式: C₃₇H₅₂O₄Si₂
• 分子量: 616.988
• InChiKey: YWMDHGUPSLPXGX-SXLOSVNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.69
• 重原子数：
  43
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,3R,4R)-3,4-bis(tert-butyldimethylsiloxy)-3,4-dihydro-2-(triphenylmethoxymethyl)-2H-pyran 在 咪唑 、 四氮唑 、 4-二甲氨基吡啶 、 偶氮二异丁腈 、 四丁基氟化铵 、 三正丁基氢锡 、 二甲基二环氧乙烷 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 氯苯 、 丙酮 、 甲苯 、 乙腈 为溶剂， 反应 311.25h， 生成 Acetic acid (2R,3S,4R,5R,6R)-2-[2-(1,5-dihydro-benzo[e][1,3,2]dioxaphosphepin-3-yloxy)-ethyl]-4,5-bis-(3-oxo-1,5-dihydro-3λ⁵-benzo[e][1,3,2]dioxaphosphepin-3-yloxy)-6-trityloxymethyl-tetrahydro-pyran-3-yl ester
  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：

  6-O-trityl-D-glucal 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以85%的产率得到(2R,3R,4R)-3,4-bis(tert-butyldimethylsiloxy)-3,4-dihydro-2-(triphenylmethoxymethyl)-2H-pyran
  参考文献：
  名称：

  通过与烯丙基甲硅烷基系链的自由基环化立体选择性地合成α-和β- C-葡萄糖苷。通过改变吡喃糖环的构象来控制立体选择性

  摘要：

  开发了一种通过与烯丙基甲硅烷基系链的自由基环化反应制备在异头位置具有3-羟丙基的1α-和1β- C-葡糖苷的有效方法。自由基环化的立体选择性可以通过吡喃糖环的构象来控制，吡喃糖环的构象可以被羟基保护基有效地操纵。

  DOI：

  10.1016/s0040-4039(00)00556-6