[(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(2,4-dioxopyrimidin-1-yl)oxolan-3-yl] diethyl phosphite | 169476-04-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(2,4-dioxopyrimidin-1-yl)oxolan-3-yl] diethyl phosphite
• CAS: 169476-04-4
• 化学式: C₂₅H₄₉N₂O₈PSi₂
• 分子量: 592.817
• InChiKey: ZCIWVLSWODSDHT-ZHHKINOHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.53
• 重原子数：
  38
• 可旋转键数：
  14
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  105
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(2,4-dioxopyrimidin-1-yl)oxolan-3-yl] diethyl phosphite 在 吡啶 、 盐酸 、 碘 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 Phosphorochloridic acid (2R,3R,4R,5R)-4-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-5-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl ester ethyl ester
  参考文献：
  名称：

  Mechanism-based inactivation of ribonuclease A

  摘要：

  The first example of a mechanism-based inhibitor of a phosphodiesterase is reported. Although the inactivation brought about by the fluoride 4 is not complete, this compound provides a useful starting point for the synthesis of other more potent inhibitors of ribonuclease A, as well as inhibitors of other nucleases. In addition, an inexpensive method is described for the synthesis of phosphate diesters that cannot be synthesized using standard phosphoramidite methodology. Phosphitylation of the target alcohol with a dialkyl chlorophosphite, followed by activation of the resulting trialkyl phosphite with It, yields an iodophosphate. The resulting iodophosphate can then be coupled to a second alcohol, phenol, or enolate to give a phosphate triester, which after subsequent deprotection affords the desired phosphate diester. The novel phosphorylation chemistry presented should greatly facilitate the synthesis of other similar mechanism-based phosphodiesterase inhibitors.

  DOI：

  10.1021/jo00126a051
• 作为产物：
  描述：

  二乙基亚磷酰氯 、 2',5'-bis-O-(tert-butyldimethylsilyl)uridine 在 吡啶 作用下， 反应 0.17h， 生成 [(2R,3R,4R,5R)-4-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(2,4-dioxopyrimidin-1-yl)oxolan-3-yl] diethyl phosphite
  参考文献：
  名称：

  Mechanism-based inactivation of ribonuclease A

  摘要：

  The first example of a mechanism-based inhibitor of a phosphodiesterase is reported. Although the inactivation brought about by the fluoride 4 is not complete, this compound provides a useful starting point for the synthesis of other more potent inhibitors of ribonuclease A, as well as inhibitors of other nucleases. In addition, an inexpensive method is described for the synthesis of phosphate diesters that cannot be synthesized using standard phosphoramidite methodology. Phosphitylation of the target alcohol with a dialkyl chlorophosphite, followed by activation of the resulting trialkyl phosphite with It, yields an iodophosphate. The resulting iodophosphate can then be coupled to a second alcohol, phenol, or enolate to give a phosphate triester, which after subsequent deprotection affords the desired phosphate diester. The novel phosphorylation chemistry presented should greatly facilitate the synthesis of other similar mechanism-based phosphodiesterase inhibitors.

  DOI：

  10.1021/jo00126a051

文献信息

• Mechanism-based inactivation of ribonuclease A
  作者：Jeffrey K. Stowell、Theodore S. Widlanski、Tatiana G. Kutateladze、Ronald T. Raines

  DOI：10.1021/jo00126a051

  日期：1995.10

  The first example of a mechanism-based inhibitor of a phosphodiesterase is reported. Although the inactivation brought about by the fluoride 4 is not complete, this compound provides a useful starting point for the synthesis of other more potent inhibitors of ribonuclease A, as well as inhibitors of other nucleases. In addition, an inexpensive method is described for the synthesis of phosphate diesters that cannot be synthesized using standard phosphoramidite methodology. Phosphitylation of the target alcohol with a dialkyl chlorophosphite, followed by activation of the resulting trialkyl phosphite with It, yields an iodophosphate. The resulting iodophosphate can then be coupled to a second alcohol, phenol, or enolate to give a phosphate triester, which after subsequent deprotection affords the desired phosphate diester. The novel phosphorylation chemistry presented should greatly facilitate the synthesis of other similar mechanism-based phosphodiesterase inhibitors.