5'-S-(4-methoxyphenyl)-5'-thiouridine | 136721-70-5

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 5'-脱氧核糖核苷
• 英文名称: 5'-S-(4-methoxyphenyl)-5'-thiouridine
• 英文别名: 1-[(2R,3R,4S,5S)-3,4-dihydroxy-5-[(4-methoxyphenyl)sulfanylmethyl]oxolan-2-yl]pyrimidine-2,4-dione
• CAS: 136721-70-5
• 化学式: C₁₆H₁₈N₂O₆S
• 分子量: 366.395
• InChiKey: BJZZZQJHGJVGCJ-NMFUWQPSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 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：

  5'-S-(4-methoxyphenyl)-5'-thiouridine 在 4-二甲氨基吡啶 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 生成 2',3'-di-O-acetyl-5'-S-(4-methoxyphenyl)thiouridine sulfoxides
  参考文献：
  名称：

  Nucleic acid-related compounds. 68. Fluorination at C5' of nucleoside 5'-thioethers with DAST/antimony(III) chloride or xenon difluoride to give 5'-S-aryl-5'-fluoro-5'-thiouridines

  摘要：

  Oxidation of 2',3'-di-O-acetyl-5'-S-(4-methoxyphenyl)-5'-thiouridine (2a) with 3-chloroperoxybenzoic acid (MCPBA) gave the diastereomeric sulfoxides 4a. Treatment of 2a with xenon difluoride or 4a with (diethylamino)sulfur trifluoride/antimony(III) chloride gave efficient conversions to the 2',3'-di-O-acetyl-5'-fluoro-5'-S-(4-methoxyphenyl)-5'-thiouridine diastereomers 6a. The stereochemistry and conformation of 6a(5'R) were established by X-ray crystallography. The alpha-fluoro thioethers were oxidized to their sulfoxide and sulfone derivatives with MCPBA, deprotected, and characterized.

  DOI：

  10.1021/jo00024a033
• 作为产物：
  描述：

  5'-chloro-O^2'_,O3'-sulfinyl-5'-deoxy-uridine 在 ammonium hydroxide 、 sodium hydride 作用下， 以 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 5'-S-(4-methoxyphenyl)-5'-thiouridine
  参考文献：
  名称：

  Nucleic acid related compounds. 66. Improved syntheses of 5′-chloro-5′-deoxy- and 5′-S-aryl(or alkyl)-5′-thionucleosides

  摘要：

  使用硫酰氯/吡啶/乙腈（0°C至室温）处理核糖核苷可基本定量形成5'-氯-5'-脱氧-2'，3'-O-亚磺酰核苷衍生物。这些对映异构的亚硫酸酯酯可以轻松地通过甲醇氨水溶液去保护基。这样就可以不使用疑似致癌物六甲基磷酰胺（HMPA）制备5'-氯-5'-脱氧核苷。在二甲基甲酰胺中，通过钠硫醇的亲核置换反应（-30°C至室温），可以高产得到5'-S-芳基（或烷基）-5'-硫代核苷。使用硫酰氯/乙腈而不是吡啶处理核糖核苷，然后进行水处理，可以得到未修饰的5'-羟基核苷的对映异构的2'，3'-O-亚磺酰核苷。文中还提到了环状亚硫酸酯立体化学的诊断NMR位移。关键词：腺苷，5'-S-芳基（或烷基）-5'-硫代核苷，5'-氯-5'-脱氧核苷，尿苷，核苷。

  DOI：

  10.1139/v91-217

文献信息

• Nucleic acid related compounds. 66. Improved syntheses of 5′-chloro-5′-deoxy- and 5′-<i>S</i>-aryl(or alkyl)-5′-thionucleosides
  作者：Morris J. Robins、Fritz Hansske、Stanislaw F. Wnuk、Tadashi Kanai

  DOI：10.1139/v91-217

  日期：1991.9.1

  Treatment of ribonucleosides with thionyl chloride/pyridine/acetonitrile (0 °C to ambient temperature) resulted in essentially quantitative formation of 5′-chloro-5′-deoxy-2′,3′-O-sulfinylnucleoside derivatives. These diastereomeric sulfite esters underwent deprotection readily with aqueous methanolic ammonia. This gave 5′-chloro-5′-deoxynucleosides without use of the suspected carcinogen, hexamethylphosphoramide (HMPA). Nucleophilic displacement with sodium thiolates in dimethylformamide (−30 °C to ambient temperature) gave 5′-S-aryl(or alkyl)-5′-thionucleosides in high yields. Treatment of ribonucleosides with thionyl chloride/acetonitrile without pyridine followed by aqueous work-up gave diastereomeric 2′,3′-O-sulfinylnucleosides with an unmodified 5′-hydroxyl group. Diagnostic NMR shifts for cyclic sulfite ester stereochemistry are noted. Key words: adenosine, 5′-S-aryl(or alkyl)-5′-thionucleosides, 5′-chloro-5′-deoxynucleosides, uridine, nucleosides.

  使用硫酰氯/吡啶/乙腈（0°C至室温）处理核糖核苷可基本定量形成5'-氯-5'-脱氧-2'，3'-O-亚磺酰核苷衍生物。这些对映异构的亚硫酸酯酯可以轻松地通过甲醇氨水溶液去保护基。这样就可以不使用疑似致癌物六甲基磷酰胺（HMPA）制备5'-氯-5'-脱氧核苷。在二甲基甲酰胺中，通过钠硫醇的亲核置换反应（-30°C至室温），可以高产得到5'-S-芳基（或烷基）-5'-硫代核苷。使用硫酰氯/乙腈而不是吡啶处理核糖核苷，然后进行水处理，可以得到未修饰的5'-羟基核苷的对映异构的2'，3'-O-亚磺酰核苷。文中还提到了环状亚硫酸酯立体化学的诊断NMR位移。关键词：腺苷，5'-S-芳基（或烷基）-5'-硫代核苷，5'-氯-5'-脱氧核苷，尿苷，核苷。
• Nucleic acid-related compounds. 68. Fluorination at C5' of nucleoside 5'-thioethers with DAST/antimony(III) chloride or xenon difluoride to give 5'-S-aryl-5'-fluoro-5'-thiouridines
  作者：Morris J. Robins、Stanislaw F. Wnuk、Khairuzzaman B. Mullah、N. Kent Dalley

  DOI：10.1021/jo00024a033

  日期：1991.11

  Oxidation of 2',3'-di-O-acetyl-5'-S-(4-methoxyphenyl)-5'-thiouridine (2a) with 3-chloroperoxybenzoic acid (MCPBA) gave the diastereomeric sulfoxides 4a. Treatment of 2a with xenon difluoride or 4a with (diethylamino)sulfur trifluoride/antimony(III) chloride gave efficient conversions to the 2',3'-di-O-acetyl-5'-fluoro-5'-S-(4-methoxyphenyl)-5'-thiouridine diastereomers 6a. The stereochemistry and conformation of 6a(5'R) were established by X-ray crystallography. The alpha-fluoro thioethers were oxidized to their sulfoxide and sulfone derivatives with MCPBA, deprotected, and characterized.