(2R,3S,4R,5R,6R)-3-acetoxy-4,5-dihydroxy-6-(triphenylmethoxymethyl)-4,5-bis(o-xyloxyphosphoryl)-2-(oxyloxyphosphorylethyl)tetrahydropyran | 299926-71-9

• 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,3S,4R,5R,6R)-3-acetoxy-4,5-dihydroxy-6-(triphenylmethoxymethyl)-4,5-bis(o-xyloxyphosphoryl)-2-(oxyloxyphosphorylethyl)tetrahydropyran
• 英文别名: [(2R,3S,4R,5R,6R)-4,5-bis[(3-oxo-1,5-dihydro-2,4,3lambda5-benzodioxaphosphepin-3-yl)oxy]-2-[2-[(3-oxo-1,5-dihydro-2,4,3lambda5-benzodioxaphosphepin-3-yl)oxy]ethyl]-6-(trityloxymethyl)oxan-3-yl] acetate；[(2R,3S,4R,5R,6R)-4,5-bis[(3-oxo-1,5-dihydro-2,4,3λ5-benzodioxaphosphepin-3-yl)oxy]-2-[2-[(3-oxo-1,5-dihydro-2,4,3λ5-benzodioxaphosphepin-3-yl)oxy]ethyl]-6-(trityloxymethyl)oxan-3-yl] acetate
• CAS: 299926-71-9
• 化学式: C₅₃H₅₃O₁₆P₃
• 分子量: 1038.92
• InChiKey: QGRUHSMSSHMPRV-PCUZIXTNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  72
• 可旋转键数：
  16
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  179
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  (2R,3S,4R,5R,6R)-3-acetoxy-4,5-dihydroxy-6-(triphenylmethoxymethyl)-4,5-bis(o-xyloxyphosphoryl)-2-(oxyloxyphosphorylethyl)tetrahydropyran 在 palladium on activated charcoal 氢气 、 三氟乙酸 、 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 14.0h， 生成 (2R,3S,4R,5R,6R)-3-hydroxy-4,5-dihydroxy-6-hydroxymethyl-4,5-diphosphoryl-2-(2-phosphorylethyl)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：

  3-(二乙氨基)-1,5-二氢-2,4,3-苯并二噁磷杂庚英 在 四氮唑 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.83h， 生成 (2R,3S,4R,5R,6R)-3-acetoxy-4,5-dihydroxy-6-(triphenylmethoxymethyl)-4,5-bis(o-xyloxyphosphoryl)-2-(oxyloxyphosphorylethyl)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

文献信息

• Synthesis of 3,7-Anhydro-<scp>d</scp>-<i>g</i><i>lycero</i>-<scp>d</scp>-<i>i</i><i>do</i>-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
  作者：Satoshi Shuto、Yumi Yahiro、Satoshi Ichikawa、Akira Matsuda

  DOI：10.1021/jo0002339

  日期：2000.9.1

  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.