5'-O-(tert-butyldimethylsilyl)-6-(hydroxymethyl)-2',3'-O-isopropylideneuridine | 195449-53-7

• 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: 5'-O-(tert-butyldimethylsilyl)-6-(hydroxymethyl)-2',3'-O-isopropylideneuridine
• 英文别名: 1-[(3aR,4R,6R,6aR)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-6-(hydroxymethyl)pyrimidine-2,4-dione
• CAS: 195449-53-7
• 化学式: C₁₉H₃₂N₂O₇Si
• 分子量: 428.558
• InChiKey: QSXDZVCVCQWVNA-DTZQCDIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.47
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  107
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5'-O-(tert-butyldimethylsilyl)-6-(hydroxymethyl)-2',3'-O-isopropylideneuridine 在 咪唑 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 戴斯-马丁氧化剂 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 80.5h， 生成 (6R,5'S)-6,5':7,5'-dianhydro-5,6-dihydro-6,5'-dihydroxy-6-(hydroxymethyl)uridine
  参考文献：
  名称：

  The 5′,6-Oxomethylene Transglycosidic Tether for Conformational Restriction of Pyrimidine Ribonucleosides. Investigation of 6-Formyl- and 6-(Hydroxymethyl)uridine 5′-Carboxaldehydes

  摘要：

  In an effort to develop a new motif for the transglycosidic tethering of the pyrimidine nucleoside framework, the 2',3'-O-isopropylidenated and unprotected versions of 6-formyl- and 6-(hydroxymethyl)uridine 5'-carboxaldehyde were prepared and these were examined for their ability to adopt 5',6-oxomethylene tethered solution structures. In aqueous solution, the 2',3'-O-isopropylidenated nucleosides readily generated spiro-dihydrouridines via proximity-induced transglycosidic intramolecular reactions. In stark contrast, their unprotected counterparts existed mainly as the untethered aldehyde hydrates. Based on these findings, the 5',6-oxomethylene transglycosidic tether appears to constitute a useful conformational restriction motif for the pyrimidine ribonucleoside flamework, but only when the 5'-OH group is functionalized. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00970-4
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 、 4-二甲氨基吡啶 、 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 22.5h， 生成 5'-O-(tert-butyldimethylsilyl)-6-(hydroxymethyl)-2',3'-O-isopropylideneuridine
  参考文献：
  名称：

  具有整合的碱基和骨干的寡核苷酸类似物。第13部分†

  摘要：

  自身互补UA和AU二核苷酸类似物41 - 45，47，48，和51 - 60通过制备的Sonogashira与6- iodouridines耦合C（5'） -ethynylated腺苷和与8- iodoadenosines C（5'） -乙炔化尿苷。二核苷酸类似物在CDCl 3溶液中缔合。的C（6 / I） -未被取代的AU二聚体51和54更喜欢抗拉伸线性双链体取向uracilyl组和形式。UA炔丙醇41和43 – 45具有持久的分子内O（5'/ I）H⋅⋅⋅N（3 / I）H-键，因此，一个顺式取向的腺嘌呤基和GT -或TG取向乙炔基部分; 它们形成波纹状线性双工。所有其他的二聚体形成特征的循环复式顺式取向的核碱基。乙炔基部分的首选方向（C（4'），C（5'）扭转角）定义了gg和乙炔基超过O（4'/ I）的构象。所述UA二聚体42,47，和48形式的Watson-Crick氢键，该AU二聚体56和58

  DOI：

  10.1002/hlca.200690259

文献信息

• Face selective 6,1′-(1-oxo)ethano bridge formation of uracil nucleosides under hypoiodite reaction conditions
  作者：Atsushi Kittaka、Hajime Kato、Hiromichi Tanaka、Yumiko Nonaka、Midori Amano、Kazuo T. Nakamura、Tadashi Miyasaka

  DOI：10.1016/s0040-4020(99)00232-x

  日期：1999.4

  Synthesis of novel spiro uracil nucleosides with an anomeric orthoester structure in a stereoselective manner under the hypoio dite reaction conditions of Heusler-Kalvoda and Suárez is fully described. While 2′-deoxy-6-(hydroxymethyl)uridine 2 and 2′-deoxy-6-[(1-hydroxy-1-methyl)ethyl]uridine 4 gave β- and α-spiro nucleosides in 43–68% yields with low selectivity (), the secondary ary alcohols 3a and

  充分描述了在Heusler-Kalvoda和Suárez的低碘反应条件下以立体选择性方式合成具有异头酯原酸酯结构的新型螺尿嘧啶核苷。2'-deoxy-6-（羟甲基）尿苷2和2'-deoxy-6-[（1-羟基-1-甲基）乙基]尿苷4以43-68％的产率得到β-和α-螺代核苷，由于低选择性（），仲醇3a和3b的化学产率为68–79％，选择性明显好于（）。在该6-（羟基）尿苷同行的方向6-8，16-17，和19似乎不仅受2'-取代基的控制，而且受C6-侧链的C7-立体中心的手性的控制，就像在2'-脱氧尿苷系列中一样。该反应的过渡态的几何形状被假定基于环化产物的X射线晶体结构20 α和24 β。
• 6-azido and 6-azidomethyl uracil nucleosides
  作者：Yahaira Reyes、Alexander Mebel、Stanislaw F. Wnuk

  DOI：10.1080/15257770.2023.2271023

  日期：2024.5.3

  Azido nucleosides have been utilized for click reactions, metabolic incorporation into cellular DNA, and fluorescent imaging of live cells. Two classes of 6-azido modified uracil nucleosides; one w...

  叠氮核苷已用于点击反应、代谢掺入细胞 DNA 以及活细胞的荧光成像。两类6-叠氮基修饰的尿嘧啶核苷；一瓦...
• C-1′ Radical-Based Approaches for the Synthesis of Anomeric Spironucleosides
  作者：Chryssostomos Chatgilialoglu、Thanasis Gimisis、Gian Piero Spada

  DOI：10.1002/(sici)1521-3765(19991001)5:10<2866::aid-chem2866>3.0.co;2-6

  日期：1999.10.1
• Synthesis of Anomeric Spiro Uracil Nucleosides with an Orthoester Structure: Stereoselective Cyclization Controlled by the C6-Substituent
  作者：Atsushi Kittaka、Hiromichi Tanaka、Hajime Kato、Yumiko Nonaka、Kazuo T Nakamura、Tadashi Miyasaka

  DOI：10.1016/s0040-4039(97)01486-x

  日期：1997.9

  Uracil nucleosides having an anomeric orthoester structure were synthesized fi om 2'-deoxy-6-(hydroxyalkyl)uridines through hypoiodite-initiated cyclization. The hydroxyalkyl substituent at the 6-position was found to control the anomeric stereochemistry (beta/alpha=7/1 similar to 1/46) of the cyclization. The transition state geometry of the reaction was postulated based on the X-ray crystallographic structure of the cyclized product 7 alpha to elucidate the observed stereoselectivity. (C) 1997 Elsevier Science Ltd.