(2'R)-2'-bromo-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)thymidine | 161972-78-7

• 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: (2'R)-2'-bromo-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)thymidine
• 英文别名: 1-[(6aR,8R,9R,9aR)-9-bromo-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]-5-methylpyrimidine-2,4-dione
• CAS: 161972-78-7
• 化学式: C₂₂H₃₉BrN₂O₆Si₂
• 分子量: 563.636
• InChiKey: QAZUXVQMPHUIAE-ANTGDGSKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.46
• 重原子数：
  33.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  91.78
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (2'R)-2'-bromo-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)thymidine 在 三乙基硼 、 氘代三正丁基锡 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以94%的产率得到(2'R)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-[2'-2H]thymidine
  参考文献：
  名称：

  Sonochemical and Triethylborane-Induced Tin Deuteride Reduction for the Highly Diastereoselective Synthesis of (2'R)-2'-Deoxy[2'-2H]ribonucleoside Derivatives

  摘要：

  For the NMR spectroscopic conformational analysis of a sugar moiety in a DNA complex with a protein or a drug, (2'R)- and/or (2'S)-2'-deoxy[2'-H-2]ribonucleoside derivatives with high purity are useful. To develop a highly diastereoselective and efficient method for the synthesis of(2'R)-2'-deoxy[2'-H-2]ribonucleoside derivatives, studies of leaving groups (OPTC, Br) at the 2' position of nucleosides, of the effects of reaction temperature on diastereoselectivity, of radical generation (ultrasound irradiation, Et(3)B) at temperatures as low as -70 degrees C, and of protecting groups for the 3' and 5' hydroxyl groups (benzoate, TPDS) of nucleosides were carried out. Bu(3)Sn(2)H-reductive deuteration of 3',5'-di-0-benzoyl-2'-bromo-2'-deoxyuridine under high-intensity ultrasound irradiation at -71 degrees C induced notably efficient deuterium incorporation to afford a highly diastereoselective 3',5'-di-0-benzoyl-2'-deoxy[2'-H-2]uridin [(2'R):(2'S) = 96:4]. The use of Et(3)B, as an alternative radical generator, toward 2'-bromo-2'-deoxy-3',5'-0-TPDS-ribonucleosides at <--70 degrees C made it feasible to perform the reaction on a preparative scale, and provided excellent diastereoselectivity (2'-deoxyadenosine, thymidine, and 2'-deoxyuridine derivatives >99:1 which were converted to (2'R)-2'-deoxy[2'-H-2]cytidine derivatives, guanosine derivative = 91:9).

  DOI：

  10.1021/jo00126a058
• 作为产物：
  描述：

  3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-5-methyluridine 在 三氟化硼乙醚 、 lithium bromide 作用下， 以 1,4-二氧六环 为溶剂， 反应 2.0h， 以96%的产率得到(2'R)-2'-bromo-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)thymidine
  参考文献：
  名称：

  Efficient Synthesis of 2′-Bromo-2′-Deoxy-3′,5′-O-TPDS-pyrimidine Nucleosides by Boron Trifluoride Catalyzed Reaction of O²,2′-Anhydro-(1-β-D-Arabinofuran0Syl)pyrimidine Nucleosides with Lithium Bromide

  摘要：

  Efficient syntheses of 2'-bromo-2'-deoxy-3',5'-O-TPDS-uridine (5a) and 1-(2-bromo-3,5-O-TPDS-beta-D-ribofuranosyl)thymine (5b) from uridine and 1-(beta-D-ribofuranosyl)thymine are described, respectively. The key step is a treatment of 3',5'-O-TPDS-O-2,2'-anhydro-1-(beta-D-arabinofuranosyl)uracil (4a) and -thymine (4b) with LiBr in the presence of BF3-OEt(2) in 1,4-dioxane at 60 degrees C to give 5a and 5b in 98%, and 96% yield, respectively.

  DOI：

  10.1080/07328319608002418