dimethyl 3'-O-tert-butyldiphenylsilyl-5'-O-isopropoxycarbonylthymidin-5'-C-ylphosphonate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: dimethyl 3'-O-tert-butyldiphenylsilyl-5'-O-isopropoxycarbonylthymidin-5'-C-ylphosphonate
• 英文别名: [(S)-[(2S,3S,5R)-3-[tert-butyl(diphenyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]-[dimethoxy(oxido)phosphaniumyl]methyl] propan-2-yl carbonate
• 化学式: C₃₂H₄₃N₂O₁₀PSi
• 分子量: 674.76
• InChiKey: IHMITAUBNQVYJG-UMNYJUJISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.38
• 重原子数：
  46
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  145
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  1-(2-deoxy-3-O-tert-butyldiphenylsilyl-β-D-erythro-pentadialdo-1,4-furanosyl)-5-methyluracil 在 二苯基膦叠氮化物 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 dimethyl 3'-O-tert-butyldiphenylsilyl-5'-O-isopropoxycarbonylthymidin-5'-C-ylphosphonate
  参考文献：
  名称：

  Nucleoside 5′-C-phosphonates: reactivity of the α-hydroxyphosphonate moiety

  摘要：

  We found that various dialkyl phosphites, dialkyl trimethylsilyl phosphites, and tris-trimethylsilyl phosphite reacted smoothly with nucleoside 5'-aldehydes to afford epimeric nucleoside 5'-C-phosphonates in high yields. A number of these compounds in both the 2'-deoxyribo and ribo series were prepared. In the case of 2'-deoxythymidine-5'-aldehyde, a thorough study was made on the influence of the 5'-hydroxyl protecting group, type of phosphite, base, and solvent, on the yield and epimeric ratio of the resulting 5'-hydroxyphosphonates. Partial stereoselectivity in favour of either R or S epimers was observed. An attempt to transform the alpha-hydroxyl of the phosphonate moiety into a halo or azido moiety was not Successful. Only intramolecular substitution reaction of the mesyloxy group for an alkoxy residue of the 2-hydroxyethyl ester took place in a low yield. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.03.008

文献信息

• Nucleoside 5′-C-phosphonates: reactivity of the α-hydroxyphosphonate moiety
  作者：Šárka Králíková、Miloš Buděšínký、Milena Masojídková、Ivan Rosenberg

  DOI：10.1016/j.tet.2006.03.008

  日期：2006.5

  We found that various dialkyl phosphites, dialkyl trimethylsilyl phosphites, and tris-trimethylsilyl phosphite reacted smoothly with nucleoside 5'-aldehydes to afford epimeric nucleoside 5'-C-phosphonates in high yields. A number of these compounds in both the 2'-deoxyribo and ribo series were prepared. In the case of 2'-deoxythymidine-5'-aldehyde, a thorough study was made on the influence of the 5'-hydroxyl protecting group, type of phosphite, base, and solvent, on the yield and epimeric ratio of the resulting 5'-hydroxyphosphonates. Partial stereoselectivity in favour of either R or S epimers was observed. An attempt to transform the alpha-hydroxyl of the phosphonate moiety into a halo or azido moiety was not Successful. Only intramolecular substitution reaction of the mesyloxy group for an alkoxy residue of the 2-hydroxyethyl ester took place in a low yield. (c) 2006 Elsevier Ltd. All rights reserved.