(4S,5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-4-hydroxy-1-oxa-spiro[4.4]nonan-2-one | 797801-36-6

• 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: (4S,5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-4-hydroxy-1-oxa-spiro[4.4]nonan-2-one
• 英文别名: (4S,5S,9R)-9-[tert-butyl(dimethyl)silyl]oxy-4-hydroxy-1-oxaspiro[4.4]nonan-2-one
• CAS: 797801-36-6
• 化学式: C₁₄H₂₆O₄Si
• 分子量: 286.444
• InChiKey: PMQNJEKEPWINQU-WDMOLILDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.61
• 重原子数：
  19
• 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：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4S,5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-4-hydroxy-1-oxa-spiro[4.4]nonan-2-one 在 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 四氯化锡 、 二异丁基氢化铝 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 3.0h， 生成 9-[(2S,4S,5R,6R)-4,6-Bis-(tert-butyl-dimethyl-silanyloxy)-1-oxa-spiro[4.4]non-2-yl]-9H-purin-6-ylamine
  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
• 作为产物：
  描述：

  (5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-1-oxa-spiro[4.4]non-3-en-2-one 在 六甲基磷酰三胺 、 ruthenium trichloride 、 sodium periodate 、 samarium diiodide 、 乙二醇 作用下， 以 四氢呋喃 、 乙酸乙酯 、 乙腈 为溶剂， 反应 0.08h， 生成 (4S,5S,6R)-6-(tert-Butyl-dimethyl-silanyloxy)-4-hydroxy-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

文献信息

• Spirocyclic Restriction of Nucleosides
  作者：Leo A. Paquette

  DOI：10.1071/ch03267

  日期：——

  The concept of spirocyclic restriction as applied broadly to the field of nucleoside mimics makes possible the generation of diastereomeric pairs configured with a syn- or anti-oriented hydroxyl substituent at C5′. The development of concise synthetic routes to spiro-fused nucleosides bearing all possible natural bases and expectedly capable of enforcing a conformation favourable for duplex formation on incorporation into oligomers represents a significant new direction in the design of antisense molecules. The present overview describes the convenient approaches that have been developed in this laboratory for accessing varied members of this class, including analogues that feature sulfur and carbon at the apical position.

  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。
• Stereochemical Features of Lewis Acid-Promoted Glycosidations Involving 4‘-Spiroannulated DNA Building Blocks
  作者：Leo A. Paquette、Christopher K. Seekamp、Alexandra L. Kahane、David G. Hilmey、Judith Gallucci

  DOI：10.1021/jo048904g

  日期：2004.10.1

  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.