[3']thymidylic acid thymidin-5'-ylester; ammonium salt | 61845-26-9

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - （3'->5'）-二核苷酸和类似物
• 英文名称: [3']thymidylic acid thymidin-5'-ylester; ammonium salt
• 英文别名: [3']Thymidylsaeure-thymidin-5'-ylester; Ammonium-Salz；azane;[(2R,3S,5R)-3-hydroxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl [(2R,3S,5R)-2-(hydroxymethyl)-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] hydrogen phosphate
• CAS: 61845-26-9
• 化学式: C₂₀H₂₇N₄O₁₂P*H₃N
• 分子量: 563.458
• InChiKey: TUUIEHHWVRHMDA-JQQQFMHGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.12
• 重原子数：
  38
• 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：
  217
• 氢给体数：
  5
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  [3']thymidylic acid thymidin-5'-ylester; ammonium salt 以 水 为溶剂， 生成
  参考文献：
  名称：

  胸苷基-(3′-5′)-5-甲基-2′-脱氧胞苷在水溶液中的光化学¶

  摘要：

  摘要 使用 254 nm 和 UV-B 辐射在水溶液中研究了二核苷单磷酸胸苷基-(3'-5')-5-甲基-2'-脱氧胞苷 (Tpm5dC) 的光化学。多种含有 5-甲基胞嘧啶 (m5C) 的二核苷酸光产物已被分离和表征。其中包括两种环丁烷二聚体 (CBD)（顺式-syn [c,s] 和反式-syn 形式）、一个 (6-4) 加合物及其相关的杜瓦异构体，以及一种产品的两种异构体，其中 m5C 部分是转化为丙烯酰胺。还形成了少量胸苷基-(3'-5')-胸苷 (TpT)，可能是二次光反应产物。此外，光产物的特征在于其中 m5C 部分丢失，从而生成 3'-胸苷酸，在糖部分的 5-羟基上被 2'-脱氧核糖酯化。C、Tpm5dC 的 CBD 很容易脱氨基形成 TpT 的相应 CBD。已经研究了这种脱氨过程的动力学；在 pH 7.4 下，反应的相应活化焓和熵分别为 73.4 kJ/mol 和 -103.5

  DOI：

  10.1562/2004-06-15-ra-201.1
• 作为产物：
  描述：

  保护胸苷 在 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 [3']thymidylic acid thymidin-5'-ylester; ammonium salt
  参考文献：
  名称：

  无核苷碱基保护的亚磷酰胺法简便合成寡脱氧核糖核苷酸

  摘要：

  已经开发了一种通过亚磷酰胺方法轻松合成寡脱氧核糖核苷酸的方法，无需对构建块进行碱基保护；它依赖于使用咪唑鎓三氟甲磺酸盐作为核苷亚磷酰胺和核苷缩合的促进剂。在溶液相中，通过使用等摩尔量的无 N 核苷亚磷酰胺和 N-未封闭核苷以高度 O 选择性的方式完成缩合，在用双（三甲基甲硅烷基）过氧化物或叔丁基过氧化氢氧化后得到, 产率 > 95% 的磷酸二核苷。在固相合成中，需要过量的亚磷酰胺进行缩合，脱氧腺苷和脱氧胞苷都进行了一定程度的N-亚磷酸化。然而，不想要的产品，可以通过在甲醇中用苯并咪唑鎓三氟甲磺酸盐短暂处理转化为不含 N 的衍生物。因此，整个过程允许化学选择性地形成核苷酸间连接。低聚物制备...

  DOI：

  10.1021/ja973731g

文献信息

• Solid-phase synthesis of backbone-modified DNA analogs by the boranophosphotriester method using new protecting groups for nucleobases
  作者：Toshihide Kawanaka、Mamoru Shimizu、Noriko Shintani、Takeshi Wada

  DOI：10.1016/j.bmcl.2008.05.053

  日期：2008.7

  Backbone-modified DNA analogs were synthesized in good yields by the boranophosphotriester method on a solid support. The oligodeoxyribonucleoside boranophosphates, protected with 2-(azidomethyl)benzoyl groups for nucleobases, were converted into DNA and its backbone-modified analogs via the corresponding H-phosphonate intermediates. A new protecting group for the O6 position of 2'-deoxyguanosine,

  通过硼三磷酸硼酸酯方法在固体载体上以高收率合成了骨架修饰的DNA类似物。用2-（叠氮甲基）苯甲酰基保护核碱基的寡脱氧核糖核苷硼酸磷酸盐通过相应的H-膦酸酯中间体被转化成DNA及其骨架修饰的类似物。还开发了2'-脱氧鸟苷的O6位置的新保护基4-叠氮基苄基（ABn）基团。通过在2-巯基乙醇存在下用MePPh2和H2O处理，可以快速去除ABn基团。
• Mellor, Ben J.; Thomas, Eric J., Journal of the Chemical Society. Perkin transactions I, 1998, # 4, p. 747 - 757
  作者：Mellor, Ben J.、Thomas, Eric J.

  DOI：——

  日期：——
• The 4-[<i>N</i>-Methyl-<i>N</i>-(2,2,2-trifluoroacetyl)amino]butyl Group as an Alternative to the 2-Cyanoethyl Group for Phosphate Protection in the Synthesis of Oligodeoxyribonucleotides
  作者：Andrzej Wilk、Andrzej Grajkowski、Lawrence R. Phillips、Serge L. Beaucage

  DOI：10.1021/jo990835w

  日期：1999.10.1

  The 4-[N-methyl-N-(2,2,2-trifluoroacetyl)amino]butyl group for phosphate protection in the synthesis of oligodeoxyribonucleotides has been developed to completely prevent nucleobase alkylation by acrylonitrile that could potentially occur upon deprotection of the traditional 2-cyanoethyl phosphate protecting group. The properties of this new phosphate protecting group were evaluated using the model phosphotriester 9. The mechanism of phosphate deprotection was studied by treating 9 with concentrated NH4OH. NMR analysis,of the deprotection reaction demonstrated that cleavage of the N-trifluoroacetyl group is rate-limiting. The resulting phosphotriester intermediate 13 was also shown to undergo rapid cyclodeesterification to produce O,O-diethyl phosphate 15 and N-methylpyrrolidine -16 (Scheme 2). Given the facile removal of the 4-[N-methyl-N-(2,2,2-trifluoroacetyl)amino]butyl phosphate protecting group under mild basic conditions, its utilization in oligonucleotide synthesis began with the preparation of the deoxyribonucleoside phosphoramidites 4a-d (Scheme 3). The coupling efficiency of 4a-d and conventional a-cyanoethyl deoxyribonucleoside phosphoramidites 24a-d was then compared in the solid-phase synthesis of the 20-mer d(ATCCGTAGCTAAGGTCATGC). As previously observed in the deprotection of 9, the 4-[N-methyl,N-(2,2,2-trifluoroacetyl)amino]butyl phosphate protecting groups were easily and completely removed from the oligonucleotide by using either concentrated NH4OH or pressurized ammonia gas. Analysis of the deprotected oligomer by polyacrylamide gel electrophoresis (Figure 3) indicated that the phosphoramidites 4a-d are as efficient as the 2-cyanoethyl phosphoramidites 24a-d in the synthesis of the 20-mer. Furthermore, following digestion of the crude 20-mer by snake venom phosphodiesterase and bacterial alkaline phosphatase, HPLC analysis showed complete hydrolysis to individual nucleosides and no detectable nucleobase modification.
• Specific Binding and Separation of Dinucleotides by Ferrocene-Modified Artificial Receptors
  作者：Masahiko Inouye、Masayoshi Takase

  DOI：10.1002/1521-3773(20010504)40:9<1746::aid-anie17460>3.0.co;2-u

  日期：2001.5.4
• TAKAKU, HIROSHI;WATANABE, TETSUO;HAMAMOTO, SHOJI, TETRAHEDRON LETT., 29,(1988) N 1, 81-84
  作者：TAKAKU, HIROSHI、WATANABE, TETSUO、HAMAMOTO, SHOJI

  DOI：——

  日期：——