2'-S-(4-methoxyphenyl)-2'-thiouridine | 85207-45-0

• 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: 2'-S-(4-methoxyphenyl)-2'-thiouridine
• 英文别名: 1-[(2R,3R,4R,5R)-4-hydroxy-5-(hydroxymethyl)-3-(4-methoxyphenyl)sulfanyloxolan-2-yl]pyrimidine-2,4-dione
• CAS: 85207-45-0
• 化学式: C₁₆H₁₈N₂O₆S
• 分子量: 366.395
• InChiKey: BBUQKQBSMMFAEO-NMFUWQPSSA-N

物化性质

• 密度：
  1.52±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  134
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2'-S-(4-methoxyphenyl)-2'-thiouridine 在 4-二甲氨基吡啶 、 二氟代氙 、 二乙胺基三氟化硫 、 三氯化锑 、 三乙胺 、 间氯过氧苯甲酸 、 三氯氧磷 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 33.5h， 生成 1-<3,5-di-O-acetyl-2-deoxy-2(S)-fluoro-2-<(4-methoxyphenyl)sulfonyl>-β-D-erythro-pentofuranosyl>-4-(1,2,4-triazol-1-yl)pyrimidin-2-one
  参考文献：
  名称：

  Nucleic acid related compounds. 73. Fluorination of uridine 2'-thioethers with xenon difluoride or (diethylamino)sulfur trifluoride. Synthesis of stable 2'-[alkyl(or aryl)sulfonyl]-2'-deoxy-2'-fluorouridines

  摘要：

  Treatment of 2,2'-anhydro-1-beta-D-arabinofuranosyluracil with thiolate anions gave the 2'-S-alkyl(and aryl)-2'-thiouridines (1). Oxidation of 3',5'-di-O-acetyl-2'-S-alkyl(and aryl)-2'-thiouridines (2) with 3-chloroperoxybenzoic acid (MCPBA) gave the diastereomeric sulfoxides 4. Treatment of 2 with XeF2 or 4 with (diethylamino)sulfur trifluoride/SbCl3 gave the diastereomeric 3',5'-di-O-acetyl-2'-S-alkyl(and aryl)-2'-fluoro-2'-thiouridines (9). These alpha-fluoro thioethers were oxidized (MCPBA) to their stable sulfone derivatives 11 that are analogues of the biologically active 2'-deoxy-2',2'-difluoro nucleosides. Stereochemistry (2'S) and conformations of the major diastereomers were established by X-ray crystallography. Efficient conversions of 11 to the cytidine alpha-fluoro sulfones 14 were achieved.

  DOI：

  10.1021/jo00034a031
• 作为产物：
  描述：

  4-甲氧基苯硫酚 、 2,2'-脱水尿苷 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 paraffin 为溶剂， 反应 24.0h， 以81%的产率得到2'-S-(4-methoxyphenyl)-2'-thiouridine
  参考文献：
  名称：

  Nucleic acid related compounds. 73. Fluorination of uridine 2'-thioethers with xenon difluoride or (diethylamino)sulfur trifluoride. Synthesis of stable 2'-[alkyl(or aryl)sulfonyl]-2'-deoxy-2'-fluorouridines

  摘要：

  Treatment of 2,2'-anhydro-1-beta-D-arabinofuranosyluracil with thiolate anions gave the 2'-S-alkyl(and aryl)-2'-thiouridines (1). Oxidation of 3',5'-di-O-acetyl-2'-S-alkyl(and aryl)-2'-thiouridines (2) with 3-chloroperoxybenzoic acid (MCPBA) gave the diastereomeric sulfoxides 4. Treatment of 2 with XeF2 or 4 with (diethylamino)sulfur trifluoride/SbCl3 gave the diastereomeric 3',5'-di-O-acetyl-2'-S-alkyl(and aryl)-2'-fluoro-2'-thiouridines (9). These alpha-fluoro thioethers were oxidized (MCPBA) to their stable sulfone derivatives 11 that are analogues of the biologically active 2'-deoxy-2',2'-difluoro nucleosides. Stereochemistry (2'S) and conformations of the major diastereomers were established by X-ray crystallography. Efficient conversions of 11 to the cytidine alpha-fluoro sulfones 14 were achieved.

  DOI：

  10.1021/jo00034a031

文献信息

• Studies toward the oxidative and reductive activation of C–S bonds in 2′-S-aryl-2ʹ-thiouridine derivatives
  作者：Ramanjaneyulu Rayala、Alain Giuglio-Tonolo、Julie Broggi、Thierry Terme、Patrice Vanelle、Patricia Theard、Maurice Médebielle、Stanislaw F. Wnuk

  DOI：10.1016/j.tet.2016.02.063

  日期：2016.4

  Studies directed toward the oxidative and reductive desulfurization of readily available 2'-S-aryl-2'-thiouridine derivatives were investigated with the prospect to functionalize the C2'-position of nucleosides. The oxidative desulfurization-difluorination strategy was successful on 2-(arylthio)alkanoate surrogates, while extension of the combination of oxidants and fluoride sources was not an efficient

  针对易于获得的2'-S-芳基-2'-硫代尿苷衍生物的氧化和还原脱硫的研究进行了研究，具有使核苷的C2'-位官能化的前景。氧化脱硫-二氟化策略在2-（芳硫基）链烷酸酯替代物上是成功的，而氧化剂和氟化物源组合的扩展当应用于2'-S-芳基-2'-硫代尿苷衍生物时不是有效的氟化方案，因此主要发生在嘧啶环的C5-卤代反应和C2'-单氟化而不脱硫的过程中。2'-芳基磺酰基-2'-脱氧尿苷及其2'-氟化类似物的循环伏安法显示，尽管在相对较高的阴极电位下，仍可能发生芳基砜部分的裂解。2'-芳基磺酰基-2'-脱氧尿苷与有机电子给体（OED）的还原-脱磺酰化主要产生碱诱导的呋喃类产物，而α-氟砜衍生物的化学（OED）和电化学还原-脱磺酰化产生2'-脱氧2'-氟尿苷和2'，3'-二氢-2'，3'-二脱氧2'-氟尿苷衍生物。这些结果提供了通过碳-硫键裂解产生C2'-阴离子的良好证据，为核苷中的还原功能化方法开辟了
• Matsuda, Akira; Miyasaka, Tadashi, Heterocycles, 1983, vol. 20, # 1, p. 55 - 58
  作者：Matsuda, Akira、Miyasaka, Tadashi

  DOI：——

  日期：——
• Nucleic acid related compounds. 73. Fluorination of uridine 2'-thioethers with xenon difluoride or (diethylamino)sulfur trifluoride. Synthesis of stable 2'-[alkyl(or aryl)sulfonyl]-2'-deoxy-2'-fluorouridines
  作者：Morris J. Robins、Khairuzzaman B. Mullah、Stanislaw F. Wnuk、N. Kent Dalley

  DOI：10.1021/jo00034a031

  日期：1992.4

  Treatment of 2,2'-anhydro-1-beta-D-arabinofuranosyluracil with thiolate anions gave the 2'-S-alkyl(and aryl)-2'-thiouridines (1). Oxidation of 3',5'-di-O-acetyl-2'-S-alkyl(and aryl)-2'-thiouridines (2) with 3-chloroperoxybenzoic acid (MCPBA) gave the diastereomeric sulfoxides 4. Treatment of 2 with XeF2 or 4 with (diethylamino)sulfur trifluoride/SbCl3 gave the diastereomeric 3',5'-di-O-acetyl-2'-S-alkyl(and aryl)-2'-fluoro-2'-thiouridines (9). These alpha-fluoro thioethers were oxidized (MCPBA) to their stable sulfone derivatives 11 that are analogues of the biologically active 2'-deoxy-2',2'-difluoro nucleosides. Stereochemistry (2'S) and conformations of the major diastereomers were established by X-ray crystallography. Efficient conversions of 11 to the cytidine alpha-fluoro sulfones 14 were achieved.