2',3'-Di-O-acetyl-5'-S-(4-methoxyphenyl)-5'-thioadenosine | 144493-94-7

• 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: 2',3'-Di-O-acetyl-5'-S-(4-methoxyphenyl)-5'-thioadenosine
• 英文别名: [(2S,3S,4R,5R)-4-acetyloxy-5-(6-aminopurin-9-yl)-2-[(4-methoxyphenyl)sulfanylmethyl]oxolan-3-yl] acetate
• CAS: 144493-94-7
• 化学式: C₂₁H₂₃N₅O₆S
• 分子量: 473.51
• InChiKey: JXCOWWSMXYUHGB-QTQZEZTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  166
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2',3'-Di-O-acetyl-5'-S-(4-methoxyphenyl)-5'-thioadenosine 在 2,3-二氯碘苯 、 potassium carbonate 、 N,N-二异丙基乙胺 作用下， 以 二乙二醇二甲醚 、 乙腈 为溶剂， 反应 52.0h， 生成 9-(2,3-di-O-acetyl-5(E)-chloro-5-deoxy-β-D-erythro-pent-4-enofuranosyl)adenine
  参考文献：
  名称：

  Nucleic acid related compounds. 76. Synthesis of 5'(E and Z)-chloro-4',5'-didehydro-5'-deoxyadenosines via chlorination and thermolysis of adenosine 5'-sulfoxides. Mechanism-based inhibition of S-adenosyl-L-homocysteine hydrolase

  摘要：

  Treatment of 2',3'-di-O-acetyl-5'-S-(4-methoxyphenyl)-5'-thioadenosine (1a), or its sulfoxides 2a(S(R)) and 3a(S(S)), with iodobenzene dichloride and potassium carbonate in acetonitrile resulted in formation of the 5'-chloro(and 5',5'-dichloro)-5'-deoxy-5'-[(4-methoxyphenyl)sulfinyl]adenosines 4a, 5a, 6a, and minor diastereomers. Deprotection of 5a gave 5'(S)-chloro-5'-deoxy-5'-[(4-methoxyphenyl)-sulfinyl(S(S))]adenosine [5b(5'S,S(S))] whose stereochemistry and conformation were established by X-ray crystallography. The alpha-chlorination of sulfoxides 2a(S(R)) and 3a (S(S)) occurred with predominant retention of configuration at sulfur. Thermolysis of the alpha-chloro sulfoxides and deprotection gave the chloromethylene derivatives. The 5'(Z)-chloro-4',5'-didehydro-5'-deoxyadenosine [9b(5'Z)] diastereomer was found to be a potent time-dependent inhibitor of S-adenosyl-L-homocysteine hydrolase.

  DOI：

  10.1021/jo00053a022
• 作为产物：
  描述：

  乙酸酐 、 5'-S-(4-methoxyphenyl)-5'-thioadenosine 在 吡啶 作用下， 反应 7.0h， 以99%的产率得到2',3'-Di-O-acetyl-5'-S-(4-methoxyphenyl)-5'-thioadenosine
  参考文献：
  名称：

  Nucleic Acid Related Compounds. 80. Synthesis of 5'-S-(Alkyl and aryl)-5'-fluoro-5'-thioadenosines with Xenon Difluoride or (Diethylamido)sulfur Trifluoride, Hydrolysis in Aqueous Buffer, and Inhibition of S-Adenosyl-L-homocysteine hydrolase by derived "Adenosine 5'-Aldehyde" Species

  摘要：

  Treatment of 5/-S-(alkyl and aryl)-5'-thioadenosine derivatives 2 with XeF2, or the corresponding sulfoxides 3 with DAST/SbCl3, gave diastereomeric 5'-fluoro compounds which were deprotected to give the 5'-S-(alkyl and aryl)-5'-fluoro-5'-thioadenosine analogues 5. Stereochemistry was established by X-ray crystallography, and F-19 NMR chemical shifts were definitive for configurationally-related 5'-fluoro diastereomers. Sulfoxidation and thermolysis afforded the fluoromethylene analogues with retained relative configuration. The nucleoside 5'-alpha-fluoro thioethers 5 underwent spontaneous hydrolysis in aqueous buffer to give derived ''adenosine 5'-aldehyde'' species which caused potent time-dependent inactivation of S-adenosyl-L-homocysteine hydrolase.

  DOI：

  10.1021/jo00082a010

文献信息

• Nucleic acid related compounds. 79. Efficient conversions of thioethers to .alpha.-fluoro thioethers with DAST or DAST/antimony(III) chloride
  作者：Morris J. Robins、Stanislaw F. Wnuk

  DOI：10.1021/jo00067a009

  日期：1993.7

  Dialkyl or alkyl aryl thioethers, including nucleoside thioethers, undergo virtually quantitative conversion to alpha-fluoro thioethers with (diethylamino)sulfur trifluoride (DAST) in dichloromethane at ambient temperature. Antimony(III) chloride catalyzes the process.