1-[(2R,4S,5R)-5-[[[(3aS,5S,6R,6aS)-5-[(propan-2-ylamino)methyl]spiro[3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole-2,1'-cyclopentane]-6-yl]oxy-[(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxyphosphinothioyl]oxymethyl]-4-[tert-butyl(dimethyl)silyl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione | 175523-04-3

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: 1-[(2R,4S,5R)-5-[[[(3aS,5S,6R,6aS)-5-[(propan-2-ylamino)methyl]spiro[3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole-2,1'-cyclopentane]-6-yl]oxy-[(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxyphosphinothioyl]oxymethyl]-4-[tert-butyl(dimethyl)silyl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 175523-04-3
• 化学式: C₄₅H₇₆N₅O₁₄PSSi₂
• 分子量: 1030.33
• InChiKey: IGZMLVNDIYBLPA-IRSPCIAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.11
• 重原子数：
  68
• 可旋转键数：
  19
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  235
• 氢给体数：
  3
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  1-[(2R,4S,5R)-5-[[[(3aS,5S,6R,6aS)-5-[(propan-2-ylamino)methyl]spiro[3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole-2,1'-cyclopentane]-6-yl]oxy-[(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxyphosphinothioyl]oxymethyl]-4-[tert-butyl(dimethyl)silyl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione 在 三氟乙酸 作用下， 以 水 为溶剂， 反应 2.0h， 以94%的产率得到RP-thymidylyl-3',5'-thymidine phosphoromonothiolate
  参考文献：
  名称：

  Stereoselective Synthesis of Dithymidine Phosphorothioates Using Xylose Derivatives as Chiral Auxiliaries

  摘要：

  1,2-O-Cyclopentylidene-5-deoxy-5-isopropylamino-alpha-D-xylofuranose 1 and its enantiomer 11 were used as chiral auxiliaries to form, respectively, Sp and Rp dithymidine phosphorothioates 9 and 10 in 98% diastereomeric excess, using phosphoramidite methodology and 2-bromo-4,5-dicyanoimidazole as catalyst. The stereochemistry of the coupling reaction is discussed.

  DOI：

  10.1021/jo972318o
• 作为产物：
  描述：

  L-xylopyranose 在 吡啶 、 苯基二硫化物 、 对甲苯磺酸 、 溶剂黄146 、 三乙胺 、 2-溴-4,5-二氰基咪唑 、 三氯化磷 、 原甲酸三甲酯 作用下， 以 1,4-二氧六环 、 氘代氯仿 为溶剂， 反应 3.0h， 生成 1-[(2R,4S,5R)-5-[[[(3aS,5S,6R,6aS)-5-[(propan-2-ylamino)methyl]spiro[3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole-2,1'-cyclopentane]-6-yl]oxy-[(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxyphosphinothioyl]oxymethyl]-4-[tert-butyl(dimethyl)silyl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
  参考文献：
  名称：

  以手性亚磷酰胺为中间体的立体选择性合成二核苷酸硫代磷酸酯的方法

  摘要：

  1,2-二-O-环戊叉基-5-异丙基氨基-D-木呋喃糖4和其对映体ent-4被用作手性助剂，使用亚磷酰胺分别形成Rp和Sp二核苷酸硫代磷酸酯11和12，其非对映体过量为98％。方法和2-溴-4,5-二氰基咪唑作为催化剂。

  DOI：

  10.1016/0040-4039(95)02355-0

文献信息

• A stereoselective synthesis of dinucleotide phosphorothioates, using chiral phosphoramidites as intermediates
  作者：Yi Jin、Giancarlo Biancotto、George Just

  DOI：10.1016/0040-4039(95)02355-0

  日期：1996.2

  1,2-Di-O-cyclopentylidene-5-isopropylamino-D-xylofuranose 4 and its enantiomer ent-4 were used as chiral auxiliaries to form, respectively, Rp and Sp dinucleotide phosphorothioates 11 and 12 in 98% diastereomeric excess, using phosphoramidite methodology and 2-bromo-4,5-dicyanoimidazole as catalyst.

  1,2-二-O-环戊叉基-5-异丙基氨基-D-木呋喃糖4和其对映体ent-4被用作手性助剂，使用亚磷酰胺分别形成Rp和Sp二核苷酸硫代磷酸酯11和12，其非对映体过量为98％。方法和2-溴-4,5-二氰基咪唑作为催化剂。
• Stereoselective Synthesis of Dithymidine Phosphorothioates Using Xylose Derivatives as Chiral Auxiliaries
  作者：Yi Jin、George Just

  DOI：10.1021/jo972318o

  日期：1998.5.1

  1,2-O-Cyclopentylidene-5-deoxy-5-isopropylamino-alpha-D-xylofuranose 1 and its enantiomer 11 were used as chiral auxiliaries to form, respectively, Sp and Rp dithymidine phosphorothioates 9 and 10 in 98% diastereomeric excess, using phosphoramidite methodology and 2-bromo-4,5-dicyanoimidazole as catalyst. The stereochemistry of the coupling reaction is discussed.