8,5'-anhydro-2',3'-O-isopropylidene-8-mercaptoadenosine | 20789-79-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: 8,5'-anhydro-2',3'-O-isopropylidene-8-mercaptoadenosine
• 英文别名: 8,5'-S-Cycloadenosin；exo-8,5'-Anhydro-2',3'-isopropyliden-8-mercapto-adenosin；O^2'_,O3'-isopropylidene-8,5'-sulfanediyl-5'-deoxy-adenosine；(4S)-2,2-dimethyl-(3at,13at)-4,5,13,13a-tetrahydro-3aH-4r,13c-epioxido-[1,3]dioxolo[4',5':5,6][1,3]thiazocino[3,2-e]purin-8-ylamine；(1R,13S,14S,18R)-16,16-dimethyl-15,17,19-trioxa-11-thia-2,4,6,9-tetrazapentacyclo[11.5.1.02,10.03,8.014,18]nonadeca-3,5,7,9-tetraen-7-amine
• CAS: 20789-79-1
• 化学式: C₁₃H₁₅N₅O₃S
• 分子量: 321.36
• InChiKey: IPPAOQNZSWPASP-IOSLPCCCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  123
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  8,5'-anhydro-2',3'-O-isopropylidene-8-mercaptoadenosine 在 三正丁胺 、 水 、 溶剂黄146 、 sodium nitrite 、 三氯氧磷 作用下， 生成 (4S)-8-chloro-2,2-dimethyl-(3at,13at)-4,5,13,13a-tetrahydro-3aH-4r,13c-epioxido-[1,3]dioxolo[4',5':5,6][1,3]thiazocino[3,2-e]purine
  参考文献：
  名称：

  Studies of Nucleosides and Nucleotides. LVII. Purine Cyclonucleosides. (20). Synthesis and Reactions of 8, 5'-S-Cycloadenosine Derivatives

  摘要：

  从2'、3'-异丙叉-8,5'-脱水-8-巯基肌苷（II）开始，通过用亚硝酸钠脱氨基，从相应的腺苷衍生物（I）合成各种6-取代的类似物。化合物（II）通过与POCl3和三正丁胺在回流温度下反应转化为6-氯嘌呤衍生物（III），产率为75%。化合物（III）与甲胺、二甲胺或甲基硫醇钠反应，分别得到N6-甲基（IV）、N6-二甲基（IX）和6-巯基（X）衍生物。这些化合物的紫外光谱、圆二色性和质谱图如下。化合物（IV）也可以通过在pH值为8-9的氢氧化钠溶液中加热I的N1-甲基衍生物，进行Dimroth型重排来获得。未保护的1-甲基腺苷-8,5'-S-环核苷也发生了相同类型的重排，得到化合物（VIII）。

  DOI：

  10.1248/cpb.22.1313
• 作为产物：
  描述：

  8-溴膘苷 在 对甲苯磺酸 、 硫脲 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 4.08h， 生成 8,5'-anhydro-2',3'-O-isopropylidene-8-mercaptoadenosine
  参考文献：
  名称：

  Nucleosides VI: A Novel and Convenient Synthesis of PurineS-Cyclonucleosides Via Mitsunobu Reaction

  摘要：

  Two representative S-cyclonucleosides, 8,5'-anhydro-2', 3'-O-isopropylidene-8-mercaptoadenosine (3) and 8,2'-anhydro-3',5'-O-(tetraisopropyldisiloxane-1,3-diyl)-8-mercaptoguanosine (8), were prepared in good yields by dropwise addition of one equivalent each of triphenylphosphine and DEAD in DMF into a mixture of 2',3'-O-isopropylidene-8-mercaptoadenosine (2) or 3',5'-O-(tetra-iso-propyldisiloxane-1,3-diyl)-8-mercaptoguanosine (7), respectively, in DMF. Treatment of compound 2 with two equivalents each of triphenylphosphine and DEAD in DMF afforded N-[8,5'-anhydro-2',3'-0-isopropylidene-8-mercaptopurin-6-yl]triphenylphospha-lambda5-azene (4) in 87% yield.

  DOI：

  10.1080/07328319308018564

文献信息

• Nucleosides VI: A Novel and Convenient Synthesis of Purine<i>S</i>-Cyclonucleosides Via Mitsunobu Reaction
  作者：Ji-Wang Chern、Chia-Chi Kuo、Ming-Jyh Chang、Lee-Tai Liu

  DOI：10.1080/07328319308018564

  日期：1993.11

  Two representative S-cyclonucleosides, 8,5'-anhydro-2', 3'-O-isopropylidene-8-mercaptoadenosine (3) and 8,2'-anhydro-3',5'-O-(tetraisopropyldisiloxane-1,3-diyl)-8-mercaptoguanosine (8), were prepared in good yields by dropwise addition of one equivalent each of triphenylphosphine and DEAD in DMF into a mixture of 2',3'-O-isopropylidene-8-mercaptoadenosine (2) or 3',5'-O-(tetra-iso-propyldisiloxane-1,3-diyl)-8-mercaptoguanosine (7), respectively, in DMF. Treatment of compound 2 with two equivalents each of triphenylphosphine and DEAD in DMF afforded N-[8,5'-anhydro-2',3'-0-isopropylidene-8-mercaptopurin-6-yl]triphenylphospha-lambda5-azene (4) in 87% yield.
• Studies of Nucleosides and Nucleotides. LVII. Purine Cyclonucleosides. (20). Synthesis and Reactions of 8, 5'-S-Cycloadenosine Derivatives
  作者：MORIO IKEHARA、YASUYUKI MATSUDA

  DOI：10.1248/cpb.22.1313

  日期：——

  Starting from 2', 3'-isopropylidene-8, 5'-anhydro-8-mercaptoinosine (II), synthesized from the corresponding adenosine derivative (I) by deamination with sodium nitrite, various 6-substituted analogs were synthesized. Compound (II) was converted to 6-chloropurine derivative (III) by the reaction with POCl3 and tri-n-butylamine at refluxing temperature in 75% yield. Compound (III) was allowed to react either with methylamine, dimethylamine or sodium methylmercaptide to give N6-methyl (IV), N6-dimethyl (IX) and 6-methylmercapto (X) derivatives, respectively. Ultraviolet spectrum, circular dichroism and mass spectra of these compounds are listed. Compound (IV) was alternatively obtained by a Dimroth type rearrangement of N1-methyl derivative of I by heating in sodium hydroxide solution at pH 8-9. The same type of rearrangement occured also with unprotected 1-methyladenosine-8, 5'-S-cyclonucleoside to give compound (VIII).

  从2'、3'-异丙叉-8,5'-脱水-8-巯基肌苷（II）开始，通过用亚硝酸钠脱氨基，从相应的腺苷衍生物（I）合成各种6-取代的类似物。化合物（II）通过与POCl3和三正丁胺在回流温度下反应转化为6-氯嘌呤衍生物（III），产率为75%。化合物（III）与甲胺、二甲胺或甲基硫醇钠反应，分别得到N6-甲基（IV）、N6-二甲基（IX）和6-巯基（X）衍生物。这些化合物的紫外光谱、圆二色性和质谱图如下。化合物（IV）也可以通过在pH值为8-9的氢氧化钠溶液中加热I的N1-甲基衍生物，进行Dimroth型重排来获得。未保护的1-甲基腺苷-8,5'-S-环核苷也发生了相同类型的重排，得到化合物（VIII）。