p-tolyl-3-O-acetyl-1-thio-5-O-triisopropylsilyl-2-deoxy-β-D-ribofuranoside | 1402737-55-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: p-tolyl-3-O-acetyl-1-thio-5-O-triisopropylsilyl-2-deoxy-β-D-ribofuranoside
• 英文别名: [(2R,3S,5S)-5-(4-methylphenyl)sulfanyl-2-[tri(propan-2-yl)silyloxymethyl]oxolan-3-yl] acetate
• CAS: 1402737-55-6
• 化学式: C₂₃H₃₈O₄SSi
• 分子量: 438.704
• InChiKey: MVZYKOAIKCIPQX-ZRBLBEILSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.33
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  70.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,3,5-tri-O-acetyl-2-deoxyribose 在 咪唑 、 4-二甲氨基吡啶 、 potassium carbonate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 33.41h， 生成 p-tolyl-3-O-acetyl-1-thio-5-O-triisopropylsilyl-2-deoxy-α-D-ribofuranoside 、 p-tolyl-3-O-acetyl-1-thio-5-O-triisopropylsilyl-2-deoxy-β-D-ribofuranoside
  参考文献：
  名称：

  A Highly Fluorescent Nucleobase Molecular Rotor

  摘要：

  Fluorescent base analogs (FBAs) are powerful probes of nucleic acids' structures and dynamics. However, previously reported FBAs exhibit relatively low brightness and therefore limited sensitivity of detection. Here we report the hitherto brightest FBA that has ideal molecular rotor properties for detecting local dynamic motions associated with base pair mismatches. The new trans-stilbene annulated uracil derivative "T-ts" exhibits bright fluorescence emissions in various solvents (epsilon x Phi = 3400-29 700 cm(-1) M-1) and is highly sensitive to mechanical motions in duplex DNA (epsilon x Phi = 150-4250 cm(-1) M-1). T-ts is thereby a "smart" thymidine analog, exhibiting a 28-fold brighter fluorescence intensity when base paired with A as compared to T or C. Time-correlated single photon counting revealed that the fluorescence lifetime of T-t(s) (tau = 4-11 ns) was shorter than its anisotropy decay in well-matched duplex DNA (theta = 20 ns), yet longer than the dynamic motions of base pair mismatches (0.1-10 ns). These properties enable unprecedented sensitivity in detecting local dynamics of nucleic acids.

  DOI：

  10.1021/jacs.0c05180

文献信息

• Stereoselective <i>N</i>-Glycosylation of 2-Deoxythioribosides for Fluorescent Nucleoside Synthesis
  作者：Guillaume Mata、Nathan W. Luedtke

  DOI：10.1021/jo3014929

  日期：2012.10.19

  An efficient method for the N-2-deoxyribosylation of modified nucleobases by 2-deoxythioriboside donors is reported. In the presence of an in situ silylated nudeobase, thioglycosides can be activated with NIS/HOTf to give nucleosides in high yields and with good beta-selectivity. By tuning the protecting groups on the C3 and CS hydroxyls, alpha/beta ratios ranging from 1.0:4.0 to 4.5:1.0 can be obtained. This strategy is applicable to the synthesis of various nucleosides, including ring-expanded pyrimidine derivatives containing sulfur that have previously been reported in low yields. The utility of this approach is further demonstrated by the synthesis of fluorescent nucleosides analogues such as quinazoline and oxophenothiazine that should find broad utility in DNA-folding and recognition studies.
• Synthesis and Solvatochromic Fluorescence of Biaryl Pyrimidine Nucleosides
  作者：Guillaume Mata、Nathan W. Luedtke

  DOI：10.1021/ol400930s

  日期：2013.5.17

  Fluorescent pyrimidine analogs containing a fused biphenyl unit were prepared in high yields using stereoselective N-glycosylation and Suzuki-Miyaura cross-coupling reactions. The resulting "push-pull" fluorophores exhibit highly solvatochromic emissions from twisted intramolecular charge-transfer (TICT) states.