3'-deoxythymidin-3'-ylsulfamoyl-[3'(N)->5'(O)]-thymidine | 288391-07-1

• 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: 3'-deoxythymidin-3'-ylsulfamoyl-[3'(N)->5'(O)]-thymidine
• 英文别名: [(2R,3S,5R)-3-hydroxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl N-[(2S,3S,5R)-2-(hydroxymethyl)-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]sulfamate
• CAS: 288391-07-1
• 化学式: C₂₀H₂₇N₅O₁₁S
• 分子量: 545.527
• InChiKey: HSOHMACWPLOEFM-KPRKPIBOSA-N

物化性质

• 密度：
  1.67±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -2.2
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  222
• 氢给体数：
  5
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  3'-deoxythymidin-3'-ylsulfamoyl-[3'(N)->5'(O)]-thymidine 以 水 为溶剂， 反应 0.5h， 生成 (2R,4S,5R,10S,11S,13R,18R,19S)-4,18-dihydroxy-11-(hydroxymethyl)-18,24-dimethyl-8,8-dioxo-7,12,26-trioxa-8lambda6-thia-1,9,14,16,21-pentazapentacyclo[18.2.2.12,5.110,13.014,19]hexacosa-20,23-diene-15,17,22-trione 、 、 (1R,6S,7S,8R,9R,14R,16S,17S,22R,23S)-23-hydroxy-16-(hydroxymethyl)-6,9-dimethyl-19,19-dioxo-15,20,25-trioxa-19lambda6-thia-2,4,11,13,18-pentazahexacyclo[20.2.1.114,17.02,7.06,9.08,13]hexacosane-3,5,10,12-tetrone
  参考文献：
  名称：

  Crystal Structure and Photochemical Behavior in Solution of the 3‘-N-Sulfamate Analogue of Thymidylyl(3‘-5‘)thymidine

  摘要：

  [GRAPHICS]The 3'-N-sulfamate analogue of thymidylyl(3'-5')thymidine (TnsoT, 1) exhibits a preference for a C3'-endo conformation in the solution and solid states. Its photochemical behavior in solution is compared to that of its natural counterpart, thymidylyl(3'-5')thymidine (TpT, 2), to get further insight into the significance of the C3'-endo conformation on the photoproduct formation at the single-stranded dinucleotide level. Irradiation at 254 nm of 1 led to the same type of photoproducts as observed with 2. However, 1 was significantly more photoreactive than 2, and accordingly, the initial rate of photoproduct formation was enhanced in accordance with its propensity to base stack compared to 2. The corresponding quantum yields were determined and showed that the enhancement factor (1 compared to 2) is moderate for the cyclobutane pyrimidine dimer (CPD) (1.26) and much higher for the (6-4) photoproduct (1.8). These data strongly suggest that the CPD and (6-4) photoproduct arise from distinct minor stacked conformations.

  DOI：

  10.1021/jo061488a
• 作为产物：
  描述：

  3'-O-acetylthymidine 在 4 A molecular sieve 、 溶剂黄146 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 27.0h， 生成 3'-deoxythymidin-3'-ylsulfamoyl-[3'(N)->5'(O)]-thymidine
  参考文献：
  名称：

  Crystal Structure and Photochemical Behavior in Solution of the 3‘-N-Sulfamate Analogue of Thymidylyl(3‘-5‘)thymidine

  摘要：

  [GRAPHICS]The 3'-N-sulfamate analogue of thymidylyl(3'-5')thymidine (TnsoT, 1) exhibits a preference for a C3'-endo conformation in the solution and solid states. Its photochemical behavior in solution is compared to that of its natural counterpart, thymidylyl(3'-5')thymidine (TpT, 2), to get further insight into the significance of the C3'-endo conformation on the photoproduct formation at the single-stranded dinucleotide level. Irradiation at 254 nm of 1 led to the same type of photoproducts as observed with 2. However, 1 was significantly more photoreactive than 2, and accordingly, the initial rate of photoproduct formation was enhanced in accordance with its propensity to base stack compared to 2. The corresponding quantum yields were determined and showed that the enhancement factor (1 compared to 2) is moderate for the cyclobutane pyrimidine dimer (CPD) (1.26) and much higher for the (6-4) photoproduct (1.8). These data strongly suggest that the CPD and (6-4) photoproduct arise from distinct minor stacked conformations.

  DOI：

  10.1021/jo061488a

文献信息

• Synthesis and nucleic-acid-binding properties of sulfamide- and 3′-N-sulfamate-modified DNAElectronic supplementary information (ESI) available: typical melting curves obtained from thermal denaturation of modified oligonucleotides with complementary DNA and RNA. See http://www.rsc.org/suppdata/p1/b1/b110603c/
  作者：Kevin J. Fettes、Nigel Howard、David T. Hickman、Steven Adah、Mark R. Player、Paul F. Torrence、Jason Micklefield

  DOI：10.1039/b110603c

  日期：2002.2.6

  A novel synthetic route for the preparation of sulfamide- and 3′-N-sulfamate-modified dinucleosides has been developed. The synthesis utilises 4-nitrophenyl chlorosulfate to prepare 4-nitrophenyl 3′- or 5′-sulfamates (e.g., 18 and 27), which couple smoothly with the alcohol or amine functionalities of other nucleosides. The conformational properties of the sulfamide- and 3′-N-sulfamate-modified dinucleosides

  已开发出一种新的合成路线，用于制备磺酰胺和3'- N-氨基磺酸酯修饰的二核苷。的合成利用4-硝基苯基氯磺酸以制备4-硝基苯基3'-或5'-氨基磺酸酯（例如，18和27），其联接平稳地与其他核苷的醇或胺官能团。使用NMR和CD光谱比较了磺酰胺和3'- N-氨基磺酸酯修饰的二核苷d（TnsnT）和d（TnsoT）的构象性质与天然二核苷酸d（TpT）。虽然两种修饰导致从C2'- 5'-末端核糖环的构象平衡的移位内切到一个优选的C3'-内切构象，只有3'- N-氨基磺酸酯修饰的二聚体显示出采用碱基堆积的螺旋构象的倾向增加。将磺酰胺和3'- N-氨基磺酸酯修饰掺入DNA序列d（GCGT 10 GCG）中，可以使用UV热变性实验确定双链体的解链温度。这表明，磺酰胺修饰显着破坏了互补DNA和RNA的双链体的稳定性。然而，3'- N-氨基磺酸盐修饰对双链体稳定性几乎没有影响，甚至在低盐浓度下也能稳定DNA双链体。这些结果表明3'-
• Replacement of the phosphodiester linkage in DNA with sulfamide and 3′-N-sulfamate groups
  作者：Kevin J. Fettes、Nigel Howard、David T. Hickman、Steven A. Adah、Mark R. Player、Paul F. Torrence、Jason Micklefield

  DOI：10.1039/b001586p

  日期：——

  Replacing phosphodiester linkages in DNA with neutral 3′-N-sulfamate groups has little effect on the binding affinity for complementary DNA or RNA, whereas incorporation of sulfamide groups into DNA results in considerable destabilisation of isosequential duplexes.

  用中性取代 DNA 中的磷酸二酯键 3-N-氨基磺酸基团对结合影响很小 与互补 DNA 或 RNA 的亲和力，而掺入磺酰胺 DNA 中的基团导致等序列的相当大的不稳定 复式公寓。
• Crystal Structure and Photochemical Behavior in Solution of the 3‘-<i>N</i>-Sulfamate Analogue of Thymidylyl(3‘-5‘)thymidine
  作者：Céline Moriou、Martial Thomas、Marie-Thérèse Adeline、Marie-Thérèse Martin、Angèle Chiaroni、Sylvie Pochet、Jean-Louis Fourrey、Alain Favre、Pascale Clivio

  DOI：10.1021/jo061488a

  日期：2007.1.1

  [GRAPHICS]The 3'-N-sulfamate analogue of thymidylyl(3'-5')thymidine (TnsoT, 1) exhibits a preference for a C3'-endo conformation in the solution and solid states. Its photochemical behavior in solution is compared to that of its natural counterpart, thymidylyl(3'-5')thymidine (TpT, 2), to get further insight into the significance of the C3'-endo conformation on the photoproduct formation at the single-stranded dinucleotide level. Irradiation at 254 nm of 1 led to the same type of photoproducts as observed with 2. However, 1 was significantly more photoreactive than 2, and accordingly, the initial rate of photoproduct formation was enhanced in accordance with its propensity to base stack compared to 2. The corresponding quantum yields were determined and showed that the enhancement factor (1 compared to 2) is moderate for the cyclobutane pyrimidine dimer (CPD) (1.26) and much higher for the (6-4) photoproduct (1.8). These data strongly suggest that the CPD and (6-4) photoproduct arise from distinct minor stacked conformations.