3'-O-tert-butyldiphenylsilyl-5'-(R)-C-dimethylphosphonothymidine | 264141-41-5

• 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: 3'-O-tert-butyldiphenylsilyl-5'-(R)-C-dimethylphosphonothymidine
• 英文别名: dimethyl 3'-O-tert-butyldiphenylsilylthymidin-5'-C-ylphosphonate；1-[(2R,4S,5S)-4-[tert-butyl(diphenyl)silyl]oxy-5-[(R)-[dimethoxy(oxido)phosphaniumyl]-hydroxymethyl]oxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 264141-41-5
• 化学式: C₂₈H₃₇N₂O₈PSi
• 分子量: 588.67
• InChiKey: SZVBZDCDJXNPSG-CONSUNNSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.81
• 重原子数：
  40
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  130
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  偶氮二甲酸二异丙酯 、 3'-O-tert-butyldiphenylsilyl-5'-(R)-C-dimethylphosphonothymidine 在 二苯基膦叠氮化物 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 dimethyl 3'-O-tert-butyldiphenylsilyl-5'-O-isopropoxycarbonylthymidin-5'-C-ylphosphonate 、 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
• 作为产物：
  描述：

  1-[(2R,4S,5R)-4-(tert-butyldiphenylsilanyloxy)-5-hydroxymethyltetrahydrofuran-2-yl]-5-methyl-1H-pyrimidine-2,4-dione 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.58h， 生成 3'-O-tert-butyldiphenylsilyl-5'-(R)-C-dimethylphosphonothymidine
  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

• Geminal hydroxy phosphonate derivatives of nucleosides: A novel class of nucleoside 5′-monophosphate analogues
  作者：Šárka Králı́ková、Miloš Budĕšı́nský、Milena Masojı́dková、Ivan Rosenberg

  DOI：10.1016/s0040-4039(99)02107-3

  日期：2000.2

  A novel type of phosphonate-based, isopolar, nonisosteric 5′-nucleotide analogue, the nucleoside 5′-hydroxy phosphonates, was prepared by Abramov nucleophilic addition of various phosphorous acid esters to nucleoside 5′-aldehydes. The newly formed compounds are distinguished by chirality of the 5′-carbon atom. The configuration of the 5′-epimers was assigned from NMR spectra.

  通过将各种亚磷酸酯亲核加成到核苷5'-醛上，制备了一种新型的基于膦酸酯的，等极性，非等规的5'-核苷酸类似物，核苷5'-羟基膦酸酯。新形成的化合物的特征在于5'-碳原子的手性。5'-差向异构体的构型由NMR光谱确定。