TpsT | 200335-37-1

• 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: TpsT
• 英文别名: 1-[(2R,4S,5R)-4-hydroxy-5-[[hydroxy-[(2R,3S,5R)-2-(hydroxymethyl)-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-sulfidophosphaniumyl]oxymethyl]oxolan-2-yl]-5-methyl-2-oxopyrimidin-4-olate
• CAS: 200335-37-1
• 化学式: C₂₀H₂₆N₄O₁₁PS
• 分子量: 561.486
• InChiKey: BAYJGGZTPVYYDX-GOBUZWBYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.5
• 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：
  231
• 氢给体数：
  4
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  TpsT 在 1,3,5-三丙烯酰基六氢-1,3,5-三嗪 、 碘 、 三乙胺 作用下， 以 吡啶 为溶剂， 反应 0.08h， 生成 dithymidylyl-3',5'-phosphorofluoridate
  参考文献：
  名称：

  A Mild Method for the Preparation of Nucleoside Phosphorofluoridate and Phosphorofluoridothioate Diesters

  摘要：

  Synthesis of unprotected dinucleoside phosphorofluoridate and phosphorofluoridothioates from the corresponding phosphororthioate and phosphorodithioate derivatives is described.

  DOI：

  10.1080/07328319908044677
• 作为产物：
  描述：

  3'-O-acetylthymidine 在 乙酸铵 、 ammonium hydroxide 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 triethylamine tris(hydrogen fluoride) 作用下， 以 水 、 乙腈 为溶剂， 反应 20.0h， 生成 TpsT
  参考文献：
  名称：

  Misiura, Konrad; Szymanowicz, Daria; Stec, Wojciech J., Collection of Czechoslovak Chemical Communications, 1996, vol. 61, p. S101 - S106

  摘要：

  DOI：

文献信息

• Thermolytic 4-Methylthio-1-butyl Group for Phosphate/Thiophosphate Protection in Solid-Phase Synthesis of DNA Oligonucleotides
  作者：Jacek Cieślak、Andrzej Grajkowski、Victor Livengood、Serge L. Beaucage

  DOI：10.1021/jo035861f

  日期：2004.4.1

  phosphate/thiophosphate protecting group for DNA oligonucleotides has been investigated for its potential application to a “heat-driven” process for either oligonucleotide synthesis on diagnostic microarrays or, oppositely, to the large-scale preparation of therapeutic oligonucleotides. The preparation of phosphoramidites 10a−d is straightforward, and the incorporation of these amidites into oligonucleotides via solid-phase

  已经研究了用于DNA寡核苷酸的不耐热的4-甲基硫基-1-丁基磷酸酯/硫代磷酸酯保护基团，其在诊断芯片上合成寡核苷酸的“热驱动”过程中具有潜在的应用潜力，或者相反，在大规模制备寡核苷酸时具有潜在的应用价值。治疗性寡核苷酸。亚磷酰胺10a - d的制备这是很简单的，并且通过固相技术将这些亚酰胺掺入寡核苷酸的过程与使用2-氰基乙基脱氧核糖核苷亚磷酰胺所实现的过程一样有效。4-甲基硫基-1-丁基磷酸酯/硫代磷酸酯保护基的多功能性可通过在中性条件下于55°C在中性条件下于55°C的水性缓冲液中加热30分钟或在55°C的浓缩条件下2小时内从寡核苷酸中轻松去除而获得。 NH 4 OH。脱保护反应通过分子内环脱酯化机理发生，导致形成salt盐18。与脱氧核糖核苷和N混合时在近似于大规模（> 50 mmol）寡核苷酸脱保护反应的条件下，在保护的2'-脱氧核糖核苷或模型硫代磷酸酯二酯的作用下，盐18不会显着改
• Synthesis of dinucleoside phosphates and their analogs by the boranophosphotriester method using azido-based protecting groups
  作者：Toshihide Kawanaka、Mamoru Shimizu、Takeshi Wada

  DOI：10.1016/j.tetlet.2007.01.064

  日期：2007.3

  backbone-modified analogs were synthesized in good yields by the boranophosphotriester method in solution. The oligodeoxyriobonucleoside boranophosphates, fully protected with 2-(azidomethyl)benzoyl groups, were converted to the various backbone-modified DNA analogs via the corresponding H-phosphonate intermediates. A new efficient protecting group for the O6-position of 2′-deoxyguanosine, 4-[(2-azidom

  通过硼三磷酸硼酸酯方法在溶液中以高收率合成了寡脱氧核糖核苷酸及其骨架修饰的类似物。用2-（叠氮基甲基）苯甲酰基充分保护的寡脱氧核糖核苷硼酸磷酸酯通过相应的H-膦酸酯中间体转化为各种骨架修饰的DNA类似物。还开发了一种新的2'-脱氧鸟苷的O 6位有效保护基，即4-[（（2-叠氮基甲基）苯甲酰氧基]苄基（AZBn）。发现通过在二恶烷–2-巯基乙醇–H 2 O中用MePPh 2处理可以快速去除AZBn组。
• Kinetic and Theoretical Studies on the Mechanism of Alkaline Hydrolysis of DNA
  作者：Naoya Takeda、Masahiko Shibata、Nobuo Tajima、Kimihiko Hirao、Makoto Komiyama

  DOI：10.1021/jo000323d

  日期：2000.7.1

  hydrolysis of thymidine 3'-monophosphate esters (including thymidylyl(3'-5')thymidine (Tp-OT)) monotonically decrease as the leaving groups get poorer. According to the theoretical calculation in which the solvent effects are incorporated, no intermediate is formed in the course of the reaction. In the alkaline hydrolysis of the activated Tp-OT analogues having good leaving groups, the 3',5'-cyclic monophosphate

  通过动力学分析和密度泛函理论计算研究了碱水解DNA的反应机理。胸苷3'-单磷酸酯（包括胸苷基（3'-5'）胸苷（Tp-OT））的水解速率随着离去基团的变差而单调降低。根据结合了溶剂作用的理论计算，在反应过程中没有形成中间体。在具有良好离去基团的活化的Tp-OT类似物的碱性水解中，通过5'-烷氧基离子通过分子内攻击同时形成了胸苷的3'，5'-环单磷酸。但是，在天然二核苷酸的水解中，不会发生这种副反应，因为由于构象约束而不能形成导致其贫穷的离开群体离开的过渡状态。对磷酸二甲酯及其O（桥基）-> S取代类似物水解的理论分析支持了这些观点。
• Allyl Group as a Protecting Group for Internucleotide Phosphate and Thiophosphate Linkages in Oligonucleotide Synthesis:  Facile Oxidation and Deprotection Conditions
  作者：Muthiah Manoharan、Yixin Lu、Martin D. Casper、George Just

  DOI：10.1021/ol9910518

  日期：2000.2.1

  [reaction: see text] The allyl group, which serves as a protecting group for an internucleotide bond for both phosphates and phosphorothioates, can be easily removed by good nucleophiles under weakly basic or neutral conditions. For a practical synthesis on solid support, camphorsulfonyloxaziridine was used as the oxidizing agent for synthesizing DNA, while the Beaucage reagent was used for preparing

  [反应：见正文]烯丙基是弱磷酸盐或硫代磷酸酯的核苷酸间键的保护基，很容易在弱碱性或中性条件下被良好的亲核试剂除去。对于在固体载体上的实际合成，将樟脑磺酰基恶二丙啶用作合成DNA的氧化剂，而Beaucage试剂用于制备硫代磷酸酯低聚物。两种类型的寡核苷酸都容易通过含有2％巯基乙醇的浓氢氧化铵去保护。
• Assessment of heat-sensitive thiophosphate protecting groups in the development of thermolytic DNA oligonucleotide prodrugs
  作者：Cristina Ausín、Jon S. Kauffman、Robert J. Duff、Shankaramma Shivaprasad、Serge L. Beaucage

  DOI：10.1016/j.tet.2009.10.096

  日期：2010.1

  Heat-sensitive thiophosphate protecting groups derived from the alcohol 4 or 10 have provided insights in the design of DNA oligonucleotide prodrugs. Indeed, functional groups stemming from the alcohol 9, 15, 16 or 22 may be applicable to thiophosphate protection of immunostimulatory CpG DNA motifs, whereas those originating from the alcohol 3, 5,12,13,18, 20 or 22 offer adequate protection of terminal phosphodiester functions against ubiquitous exonucleases that may be found in biological environments. Functional groups derived from the alcohol 9, 15, 16, 19 or 23 are suitable for the protection of phosphodiester functions flanking the CpG motifs of immunomodulatory DNA sequences. Published by Elsevier Ltd.