phenyl 3,4-bis-O-tert-butyldimethylsilyl-6-O-trityl-1-seleno-β-D-glucose | 288584-99-6

• 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: phenyl 3,4-bis-O-tert-butyldimethylsilyl-6-O-trityl-1-seleno-β-D-glucose
• 英文别名: 3,4-bis-tert-butyldimethylsilyl-6-O-trityl-1-seleno-β-D-glucose；(2S,3R,4R,5R,6R)-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-phenylselanyl-6-(trityloxymethyl)oxan-3-ol
• CAS: 288584-99-6
• 化学式: C₄₃H₅₈O₅SeSi₂
• 分子量: 790.062
• InChiKey: CQRXNTIOFYVPSU-VTDZCKIGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.89
• 重原子数：
  51
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  phenyl 3,4-bis-O-tert-butyldimethylsilyl-6-O-trityl-1-seleno-β-D-glucose 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 、 溶剂黄146 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 氯苯 、 甲苯 、 乙腈 为溶剂， 反应 309.83h， 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
• 作为产物：
  描述：

  6-O-trityl-D-glucal 在 咪唑 、 二甲基二环氧乙烷 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 phenyl 3,4-bis-O-tert-butyldimethylsilyl-6-O-trityl-1-seleno-β-D-glucose
  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

文献信息

• Stereoselective synthesis of α- and β-C-glucosides via radical cyclization with an allylsilyl tether. Control of the stereoselectivity by changing the conformation of the pyranose ring
  作者：Satoshi Shuto、Masaru Terauchi、Yumi Yahiro、Hiroshi Abe、Satoshi Ichikawa、Akira Matsuda

  DOI：10.1016/s0040-4039(00)00556-6

  日期：2000.5

  An efficient method for preparing both 1α- and 1β-C-glucosides having a 3-hydroxypropyl group at the anomeric position via a radical cyclization reaction with an allylsilyl tether was developed. The stereoselectivity of the radical cyclization can be controlled by the conformation of the pyranose ring, which is effectively manipulated by the hyroxyl protecting groups.

  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。
• A Systematic Study of <i>C</i>-Glucoside Trisphosphates as <i>myo</i>-Inositol Trisphosphate Receptor Ligands. Synthesis of β-<i>C</i>-Glucoside Trisphosphates Based on the Conformational Restriction Strategy
  作者：Masaru Terauchi、Hiroshi Abe、Stephen C. Tovey、Skarlatos G. Dedos、Colin W. Taylor、Michael Paul、Melanie Trusselle、Barry V. L. Potter、Akira Matsuda、Satoshi Shuto

  DOI：10.1021/jm051039n

  日期：2006.3.1

  Beta-C-glucoside trisphosphates having a C2 side chain (3,7-anhydro-2-deoxy-D-glycero-D-gulo-octitol 1,5,6-trisphosphate, 11) and a C3 side chain (4,8-anhydro-2,3-dideoxy-D-glycero-D-gulo-nonanitol 1,6,7-trisphosphate, 12) were designed as structurally simplified analogues of a potent D-myo-inositol 1,4,5-trisphosphate (IP3) receptor ligand, adenophostin A. Construction of the beta-C-glucosidic structure

  具有C2侧链（3,7-脱水-2-脱氧-D-甘油-D-邻-辛醇1,5,6-三三磷酸11）和C3侧链（4,8）的β-C-葡萄糖苷三磷酸酯-脱水-2,3-二脱氧-D-甘油-D-古洛诺壬醇1,6,7-三磷酸酯（12）被设计为强力D-肌醇1,4,5-三磷酸酯的结构简化类似物（ IP3）受体配体，腺苷A。构建β-C-糖苷结构的关键，是通过两种基于构象限制策略的不同方法实现的：（1）使用临时连接的硅系链进行自由基环化（2）具有异头烯丙基取代基的糖脂醇的硅烷还原。使用这些方法，成功地合成了目标β-C-糖苷三磷酸酯11和12。在一系列C-葡萄糖苷三磷酸酯上建立了结构活性关系，包括先前合成的相关化合物，这些化合物是腺磷素A的C-糖苷类似物3，其尿嘧啶同类物5，α-C-葡萄糖苷三磷酸酯7-9具有C1，C2或C3侧链，以及具有C1，C2或C3侧链的β-C-葡糖苷三磷酸酯10-12。腺苷A及其类似物的O-糖苷键被化
• Synthesis of 4,8-anhydro-d-glycero-d-ido-nonanitol 1,6,7-trisphosphate as a novel IP3 receptor ligand using a stereoselective radical cyclization reaction based on a conformational restriction strategy
  作者：Masaru Terauchi、Yumi Yahiro、Hiroshi Abe、Satoshi Ichikawa、Stephen C. Tovey、Skarlatos G. Dedos、Colin W. Taylor、Barry V.L. Potter、Akira Matsuda、Satoshi Shuto

  DOI：10.1016/j.tet.2005.02.025

  日期：2005.4

  4,8-Anhydro-D-glycero-D-ido-nonanitol 1,6,7-trisphosphate (9), designed as a novel IP3 receptor ligand having an alpha-C-glycosidic\ structure, was synthesized via a radical cyclization reaction with a temporary connecting allylsilyl group as the key-step. Phenyl 2-O-allyldimethylsilyt-3,4-bis-O-TBS-1-seleno- beta-D-glucopyranoside (10a), conformationally restricted in the unusual C-1(4)-conformation, was treated with Bu3SnH/AIBN to form the desired alpha-cyclization product 16a almost quantitatively. On the other hand, when a conformationally unrestricted O-benzyl-protected 2-O-allyldimethylsilyl -l-selenoglucoside 15 was used as the substrate, the radical reaction was not stereoselective and gave a mixture of the alpha-and beta-products. From 16a, the target C-glucoside trisphosphate 9 was synthesized via phosphorylation of the hydroxyls by the phosphoramidite method. During the synthetic study, an efficient procedure for the oxidative C-Si bond cleavage, via a nucleophilic substitution at the silicon with p-MeOPhLi followed by Fleming oxidation, was developed. The C-glycoside 9 was found to be a full agonist for Ca2+ mobilization, although its activity was weaker than that of the natural ligand IP3. Thus, the alpha-C-glucosidic structure was shown to be a useful mimic of the myo-inositol backbone of IP3. (c) 2005 Elsevier Ltd. All rights reserved.
• Efficient synthesis of β-C-glucosides via radical cyclization with a silicon tether based on the conformational restriction strategy
  作者：Masaru Terauchi、Akira Matsuda、Satoshi Shuto

  DOI：10.1016/j.tetlet.2005.07.087

  日期：2005.9

  An efficient method for preparing beta-C-glucosides using radical cyclization with a temporary connecting silicon tether was developed. In this reaction, conformational restriction of the substrates to the unusual C-1(4)-form is essential for the cyclization to occur. (c) 2005 Published by Elsevier Ltd.
• 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.