(3R,4S,5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-3,4-dihydroxy-1-oxa-spiro[4.4]nonan-2-one | 797801-35-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3R,4S,5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-3,4-dihydroxy-1-oxa-spiro[4.4]nonan-2-one
• 英文别名: (3R,4S,5S,9R)-9-[tert-butyl(dimethyl)silyl]oxy-3,4-dihydroxy-1-oxaspiro[4.4]nonan-2-one
• CAS: 797801-35-5
• 化学式: C₁₄H₂₆O₅Si
• 分子量: 302.443
• InChiKey: LKALNZYNNDLHEO-NJBDSQKTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.58
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3R,4S,5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-3,4-dihydroxy-1-oxa-spiro[4.4]nonan-2-one 在 吡啶 、 2,6-二甲基吡啶 、 samarium diiodide 、 二异丁基氢化铝 作用下， 以 六甲基磷酰三胺 为溶剂， 生成 [(4S,5R,9R)-4,9-bis[[tert-butyl(dimethyl)silyl]oxy]-1-oxaspiro[4.4]nonan-2-yl] acetate
  参考文献：
  名称：

  Spirocyclic Restriction of Nucleosides

  摘要：

  将螺环限制的概念广泛应用于核苷模拟物领域，可以生成在 C5′处配置有同步或反方向羟基取代基的非对映异构对。开发带有所有可能天然碱基的螺状融合核苷的简明合成路线，预计能在加入低聚物时形成有利于双链形成的构象，是设计反义分子的一个重要新方向。本综述介绍了本实验室为获得该类核苷的各种成员而开发的便捷方法，包括在顶端位置具有硫和碳的类似物。

  DOI：

  10.1071/ch03267
• 作为产物：
  描述：

  (5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-1-oxa-spiro[4.4]non-3-en-2-one 在 ruthenium trichloride 、 sodium periodate 作用下， 以 乙酸乙酯 、 乙腈 为溶剂， 反应 0.08h， 以75%的产率得到(3R,4S,5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-3,4-dihydroxy-1-oxa-spiro[4.4]nonan-2-one
  参考文献：
  名称：

  Stereochemical Features of Lewis Acid-Promoted Glycosidations Involving 4‘-Spiroannulated DNA Building Blocks

  摘要：

  Tin tetrachloride-catalyzed glycosidation of persilylated nucleobases with acetate donor 6 in CH2Cl2 solution followed by deprotection gave rise very predominantly to alpha-spironucleosides. These stereochemical assignments stem from the determination of NOE interactions and an X-ray crystallographic analysis of the latter product. Computational studies revealed that these results are consistent with the fact that the C5' substituent shields the beta-face of the oxonium ion involved in the coupling reaction while the C3' substituent is projected away from the alpha-underside. Attack from the more open direction is therefore kinetically favored. Entirely comparable calculations suggested that donor 19 should behave comparably. Experimentation involving this donor gave results consistent with this model although more equitable alpha/beta spironucleoside product ratios were seen when acetonitrile was employed as the reaction medium.

  DOI：

  10.1021/jo048904g