3'-O-acetylthymidine 5'-(1-thiocyclotriphosphate) | 118275-91-5

• 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-acetylthymidine 5'-(1-thiocyclotriphosphate)
• 英文别名: [(2R,3S,5R)-2-[(4,6-dihydroxy-4,6-dioxo-2-sulfanylidene-1,3,5,2lambda5,4lambda5,6lambda5-trioxatriphosphinan-2-yl)oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] acetate；[(2R,3S,5R)-2-[(4,6-dihydroxy-4,6-dioxo-2-sulfanylidene-1,3,5,2λ5,4λ5,6λ5-trioxatriphosphinan-2-yl)oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] acetate
• CAS: 118275-91-5
• 化学式: C₁₂H₁₇N₂O₁₃P₃S
• 分子量: 522.26
• InChiKey: RJUMBCCVSVHWMF-IVZWLZJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.3
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  229
• 氢给体数：
  3
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  3'-O-acetylthymidine 5'-(1-thiocyclotriphosphate) 在 ammonium hydroxide 作用下， 生成 thymidine 5'-O-(1,3-dithiotriphosphate) 、 thymidine 5'-O-(1,1-dithiotriphosphate)
  参考文献：
  名称：

  Synthesis of nucleoside 5'-O-(1,3-dithiotriphosphates) and 5'-O-(1,1-dithiotriphosphates)

  摘要：

  The synthesis of 3'-deoxy-3'-azidothymidine 5'-O-(1,3-dithiotriphosphate) (5) as the first example of a nucleoside 5'-O-(1,3-dithiotriphosphate) is described. 2-Chloro-4H-1,3,2-benzodioxaphosphorin-4-one phosphitylates the 5'-hydroxy group of 3'deoxy-3'-azidothymidine to form intermediate 1. Reaction of 1 with thiopyrophosphate (9) and sulfur results in the formation of an unseparable mixture of 3'-deoxy-3'-azidothymidine 5'-O-(1,3-dithiotriphosphate) (5) and 3'-deoxy-3'-azidothymidine 5'-O-(1,2-dithiotriphosphate) (3). Selective hydrolysis of 5 allows isolation of 3. However, reaction of 1 with P1-O-(cyanoethyl)-P1-thiopyrophosphate (8) and sulfur produced the diastereomers of 5 in good yield. Compound 8 is prepared by reaction of 3-hydroxyproprionitrile with 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one, pyrophosphate, and sulfur to yield 10, which is ring opened to 8 by reaction with ethylenediamine. Hydrolysis of this compound leads to 9. An alternative route to nucleoside 5'-O-(1,3-dithiotriphosphates) consists of reacting a nucleoside 5'-O-(1-thiocyclotriphosphate) such as 13 with Li2S. This reaction, when performed in pyridine/dioxane, leads to a mixture of the nucleoside 5'-O-(1,3-dithiotriphosphate) and the nucleoside 5'-O-(1,1-dithiotriphosphate). The latter is the only nucleotide product when the reaction is carried out in DMF.

  DOI：

  10.1021/jo00005a023
• 作为产物：
  描述：

  2-(3'-O-acetyl-2'-deoxythymidin-5'-yl)-4H-1,3,2-benzodioxaphosphorin-4-one 在 吡啶 、 三正丁胺 、 三丁基焦磷酸铵 、 sulfur 作用下， 生成 3'-O-acetylthymidine 5'-(1-thiocyclotriphosphate)
  参考文献：
  名称：

  Synthesis of nucleoside 5'-O-(1,3-dithiotriphosphates) and 5'-O-(1,1-dithiotriphosphates)

  摘要：

  The synthesis of 3'-deoxy-3'-azidothymidine 5'-O-(1,3-dithiotriphosphate) (5) as the first example of a nucleoside 5'-O-(1,3-dithiotriphosphate) is described. 2-Chloro-4H-1,3,2-benzodioxaphosphorin-4-one phosphitylates the 5'-hydroxy group of 3'deoxy-3'-azidothymidine to form intermediate 1. Reaction of 1 with thiopyrophosphate (9) and sulfur results in the formation of an unseparable mixture of 3'-deoxy-3'-azidothymidine 5'-O-(1,3-dithiotriphosphate) (5) and 3'-deoxy-3'-azidothymidine 5'-O-(1,2-dithiotriphosphate) (3). Selective hydrolysis of 5 allows isolation of 3. However, reaction of 1 with P1-O-(cyanoethyl)-P1-thiopyrophosphate (8) and sulfur produced the diastereomers of 5 in good yield. Compound 8 is prepared by reaction of 3-hydroxyproprionitrile with 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one, pyrophosphate, and sulfur to yield 10, which is ring opened to 8 by reaction with ethylenediamine. Hydrolysis of this compound leads to 9. An alternative route to nucleoside 5'-O-(1,3-dithiotriphosphates) consists of reacting a nucleoside 5'-O-(1-thiocyclotriphosphate) such as 13 with Li2S. This reaction, when performed in pyridine/dioxane, leads to a mixture of the nucleoside 5'-O-(1,3-dithiotriphosphate) and the nucleoside 5'-O-(1,1-dithiotriphosphate). The latter is the only nucleotide product when the reaction is carried out in DMF.

  DOI：

  10.1021/jo00005a023

文献信息

• LUDWIG, JANOS;ECKSTEIN, FRITZ, J. ORG. CHEM., 54,(1989) N, C. 631-635
  作者：LUDWIG, JANOS、ECKSTEIN, FRITZ

  DOI：——

  日期：——