1-(2'-deoxy-3',5'-di-O-(p-toluoyl)-β-D-erythro-ribofuranosyl)-2-thiouracil | 151503-22-9

• 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-(2'-deoxy-3',5'-di-O-(p-toluoyl)-β-D-erythro-ribofuranosyl)-2-thiouracil
• 英文别名: 1-(2-deoxy-3,5-di-O-p-toluyl-β-D-ribofuranosyl)-2-thiouracil；β-2'-deoxy-3',5'-p-toluoyl-2-thiouridine；3',5'-di-O-p-toluyl-2'-deoxy-2-thiouridine；[(2R,3S,5R)-3-(4-methylbenzoyl)oxy-5-(4-oxo-2-sulfanylidenepyrimidin-1-yl)oxolan-2-yl]methyl 4-methylbenzoate
• CAS: 151503-22-9
• 化学式: C₂₅H₂₄N₂O₆S
• 分子量: 480.541
• InChiKey: MTHBONGWBSVRBD-TUNNFDKTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  126
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-(2'-deoxy-3',5'-di-O-(p-toluoyl)-β-D-erythro-ribofuranosyl)-2-thiouracil 在 吡啶 、 4-二甲氨基吡啶 、 sodium methylate 作用下， 生成 1-(2'-deoxy-5'-O-4,4'-dimethoxytrityl-β-D-erythro-ribofuranosyl)-2-thiouracil
  参考文献：
  名称：

  将2-硫代嘧啶核苷有效脱硫为相应的4-嘧啶酮

  摘要：

  描述了制备2'-脱氧-4-嘧啶酮（dH 2 U）和2'-脱氧-5-甲基-4-嘧啶酮（dH 2 T）核苷的程序。密钥变换是通过用一个简单处理相应的2-硫代类似物的新定量脱硫米氯过苯甲酸/吡啶溶液。这些核苷的亚磷酰胺也已经合成。

  DOI：

  10.1016/s0040-4039(00)79235-5
• 作为产物：
  描述：

  1-Α-氯-3,5-二-O-对甲苯甲酰基-2-脱氧-D-呋喃核糖 、 2-trimethylsilylthio-4-trimethylsilyloxypyrimidine 在 四氯化锡 作用下， 以 1,2-二氯乙烷 为溶剂， 以94%的产率得到1-(2'-deoxy-3',5'-di-O-(p-toluoyl)-β-D-erythro-ribofuranosyl)-2-thiouracil
  参考文献：
  名称：

  将2-硫代嘧啶核苷有效脱硫为相应的4-嘧啶酮

  摘要：

  描述了制备2'-脱氧-4-嘧啶酮（dH 2 U）和2'-脱氧-5-甲基-4-嘧啶酮（dH 2 T）核苷的程序。密钥变换是通过用一个简单处理相应的2-硫代类似物的新定量脱硫米氯过苯甲酸/吡啶溶液。这些核苷的亚磷酰胺也已经合成。

  DOI：

  10.1016/s0040-4039(00)79235-5

文献信息

• 2-Thio derivatives of dUrd and 5-fluoro-dUrd and their 5'-monophosphates: synthesis, interaction with tumor thymidylate synthase, and in vitro antitumor activity
  作者：Maria Bretner、Tadeusz Kulikowski、Jolanta M. Dzik、Malgorzata Balinska、Wojciech Rode、David Shugar

  DOI：10.1021/jm00075a016

  日期：1993.11

  deblocked with MeOH-NH3 to give the desired free anomeric nucleoside pairs 1, 5 and 3, 7, respectively. These were selectively converted to the corresponding 5'-monophosphates 2, 6 and 4, 8, with the aid of the wheat shoot phosphotransferase system. Conformations of the nucleosides 1, 3, 5, 7 are deduced from 1H NMR spectra, and circular dichroism spectra for nucleotide anomeric pairs 2, 6 and 4, 8 are reported

  5-氟-2-硫尿嘧啶（11）的方便合成是基于5-氟-2-硫胞嘧啶（9）的水解脱氨基。路易斯酸催化二-TMS-5-氟-2-硫氧嘧啶（13）或二-TMS-2-硫氧嘧啶（14）与2-脱氧-3,5-二-对甲苯基-D-呋喃呋喃糖酰氯的缩合反应（15）生成3'，5'-甲苯化2'-脱氧-5-氟-2-硫代尿苷（16和18）或2'-脱氧-2-硫代尿苷（17的β-和α-端基异构体的混合物和19），将它们各自用MeOH-NH 3解封闭，分别得到所需的游离异头核苷对1、5和3、7。在小麦芽磷酸转移酶系统的帮助下，将它们选择性地转化为相应的5'-单磷酸酯2、6和4、8。由1H NMR光谱推导出核苷1、3、5、7的构象，以及核苷酸异头对2的圆二色性光谱2 报告了6和4、8。尽管beta-2-thio-dUMP（4）是一个很好的底物（Km约为10（-5）M），但是beta-5-fluoro-2-thio-dUMP（2）
• Desulfurization of 2-thiouracil nucleosides: Conformational studies of 4-pyrimidinone nucleosides
  作者：Karina Kraszewska、Iwona Kaczyńska、Stefan Jankowski、Janina Karolak-Wojciechowska、Elzbieta Sochacka

  DOI：10.1016/j.bmc.2011.02.008

  日期：2011.4

  4-Pyrimidinone ribofuranoside (H(2)o(4)U) and 4-pyrimidinone 2 '-deoxyribofuranoside (dH(2)o(4)U) were synthesized by the oxidative desulfurization of parent 2-thiouracil nucleosides with m-chloroperbenzoic acid. The crystal structures of H(2)o(4)U and dH(2)o(4)U and their conformations in solution were determined and compared with corresponding 2-thiouracil and uracil nucleosides. The absence of a large 2-thiocarbonyl/2-carbonyl group in the nucleobase moiety results in C2'-endo puckering of the ribofuranose ring (S conformer) in the crystal structure of H(2)o(4)U, which is not typical of RNA nucleosides. Interestingly, the hydrogen bonding network in the crystals of dH(2)o(4)U stabilizes the sugar moiety conformation in the C3'-endo form (N conformer), rarely found in DNA nucleosides. In aqueous solution, dH(2)o(4)U reveals a similar population of the C2'-endo conformation (65%) to that of 2'-deoxy-2-thiouridine (62%), while the 62% population of the S conformer for H(2)o(4)U is significantly different from that of the parent 2-thiouridine, for which the N conformer is dominant (71%). Such a difference may be of biological importance, as the desulfurization process of natural tRNA 2-thiouridines may occur under conditions of oxidative stress in the cell and may influence the decoding process. (C) 2011 Elsevier Ltd. All rights reserved.
• Synthesis and Biological Activity of 5-Fluoro-2-thiocytosine Nucleosides
  作者：M. Bretner、M. Balinska、K. Krawiec、B. Kierdaszuk、D. Shugar、T. Kulikowski

  DOI：10.1080/15257779508012445

  日期：1995.5.1

  Two pathways are described for the synthesis of the 2'-deoxynucleosides of 2-thiocytosine and 5-fluoro-2-thiocytosine: (a) by nucleoside condensation, (b) by amination of the corresponding nucleosides of 2,4-dithiouracil. Biological activities vs two cell systems are described. The nucleosides are moderate to weak substrates of deoxycytidine kinase and, partly as a result of this, reasonable good inhibitors of the enzyme
• A Stereoselective Synthesis of α - and β-2′-Deoxy-2-thiouridine
  作者：Robert G. Kuimelis、Håkon Hope、Krishnan P. Nambiar

  DOI：10.1080/07328319308021507

  日期：1993.8

  A stereoselective glycosylation procedure is described for the synthesis of protected alpha- and beta-2'-deoxy-2-thiouridine (dS2U) in 68% and 94% yield, respectively. Evidence is presented that suggests the reaction proceeds through a silylated thioglycoside intermediate. This intermediate undergoes an efficient S2-->N1 rearrangement mediated by SnCl4. The phosphoramidite and phosphodiester synthons and a dS2U dinucleotide are also synthesized and the X-ray structure of beta-dS2U is presented.
• Efficient desulfurization of 2-thiopyrimidine nucleosides to the corresponding 4-pyrimidinones
  作者：Robert G. Kuimelis、Krishnan P. Nambiar

  DOI：10.1016/s0040-4039(00)79235-5

  日期：1993.6

  the preparation of 2′-deoxy-4-pyrimidone (dH2U) and 2′-deoxy-5-methyl-4-pyrimidone (dH2T) nucleosides. The key transformation is a newly quantitative desulfurization of the corresponding 2-thio analogue by a brief treatment with a m-chloroperbenzoic acid/pyridine solution. The phosphoramidites of these nucleosides have also been synthesized.

  描述了制备2'-脱氧-4-嘧啶酮（dH 2 U）和2'-脱氧-5-甲基-4-嘧啶酮（dH 2 T）核苷的程序。密钥变换是通过用一个简单处理相应的2-硫代类似物的新定量脱硫米氯过苯甲酸/吡啶溶液。这些核苷的亚磷酰胺也已经合成。