(2R,3S,4R,5S,6S)-4,5-dibenzyloxy-6-benzyloxymethyl-3-hydroxy-2-[(1S)-1-hydroxyethyl]tetrahydropyran

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4R,5S,6S)-4,5-dibenzyloxy-6-benzyloxymethyl-3-hydroxy-2-[(1S)-1-hydroxyethyl]tetrahydropyran
• 英文别名: (2R,3R,4R,5R,6S)-2-[(1S)-1-hydroxyethyl]-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-ol
• 化学式: C₂₉H₃₄O₆
• 分子量: 478.585
• InChiKey: ANPRQUUDDNYLJN-OOVPJATDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  35
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-甲氧基丙烯 、 (2R,3S,4R,5S,6S)-4,5-dibenzyloxy-6-benzyloxymethyl-3-hydroxy-2-[(1S)-1-hydroxyethyl]tetrahydropyran 在 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以100%的产率得到(1R,5S,6S,8S,9R,10S)-3,3,5-trimethyl-9,10-dibenzyloxy-8-benzyloxymethyl-bicyclo[4.4.0]-2,4,7-trioxadecane
  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：

  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 苯 、 四氢呋喃 、 甲醇 为溶剂， 反应 15.33h， 生成 (2R,3S,4R,5S,6S)-4,5-dibenzyloxy-6-benzyloxymethyl-3-hydroxy-2-[(1S)-1-hydroxyethyl]tetrahydropyran 、 (2R,3S,4R,5S,6R)-4,5-dibenzyloxy-6-benzyloxymethyl-3-hydroxy-2-[(1S)-1-hydroxyethyl]tetrahydropyran 、 (2R,3S,4R,5S,6R)-4,5-dibenzyloxy-6-benzyloxymethyl-3-hydroxy-2-[(1R)-1-hydroxyethyl]tetrahydropyran 、 (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

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.