phenyl 2-O-(allyl(dimethyl)silyl)-3,4,6-tri-O-benzyl-1-seleno-β-D-glucopyranoside | 288585-01-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2-O-(allyl(dimethyl)silyl)-3,4,6-tri-O-benzyl-1-seleno-β-D-glucopyranoside
• 英文别名: [(2S,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-phenylselanyloxan-3-yl]oxy-dimethyl-prop-2-enylsilane
• CAS: 288585-01-3
• 化学式: C₃₈H₄₄O₅SeSi
• 分子量: 687.81
• InChiKey: KKLGCQPUYOGMHF-HRTJLHCRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  45
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 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：

  phenyl 2-O-(allyl(dimethyl)silyl)-3,4,6-tri-O-benzyl-1-seleno-β-D-glucopyranoside 在 potassium fluoride 、 双氧水 、 三正丁基氢锡 、 potassium hydrogencarbonate 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 为溶剂， 反应 16.0h， 生成 3-C-(3,4,6-tri-O-benzyl-β-D-glucopyranosyl)1-propanol
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1016/j.tet.2005.02.025
• 作为产物：
  描述：

  烯丙基二甲基氯硅烷 、 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， 以100%的产率得到phenyl 2-O-(allyl(dimethyl)silyl)-3,4,6-tri-O-benzyl-1-seleno-β-D-glucopyranoside
  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。
• 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.