8,2'-anhydro-8-mercaptoadenosine | 20789-80-4

• 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: 8,2'-anhydro-8-mercaptoadenosine
• 英文别名: 8,5'-Anhydro-8-mercaptoadenosine；8,5'-S-Cycloadenosin；8,5'-Thio-cycloadenosin；8,5'-S-Cycloadenosine；(8R)-4-amino-8,9,10,11-tetrahydro-7H-8r,11c-epioxido-[1,3]thiazocino[3,2-e]purine-9c,10c-diol；8,5'-sulfanediyl-5'-deoxy-adenosine；(1R,13S,14S,15R)-7-amino-16-oxa-11-thia-2,4,6,9-tetrazatetracyclo[11.2.1.02,10.03,8]hexadeca-3,5,7,9-tetraene-14,15-diol
• CAS: 20789-80-4
• 化学式: C₁₀H₁₁N₅O₃S
• 分子量: 281.295
• InChiKey: GFHWYKIGUCTZFZ-UUOKFMHZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.2
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  145
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  8,2'-anhydro-8-mercaptoadenosine 在 barium nitrite 作用下， 以 水 、 溶剂黄146 为溶剂， 生成 8,5'-sulfanediyl-5'-deoxy-inosine
  参考文献：
  名称：

  Ikehara,M.; Muraoka,M., Chemical and pharmaceutical bulletin, 1972, vol. 20, p. 550 - 558

  摘要：

  DOI：
• 作为产物：
  描述：

  8-溴膘苷 在 Dowex-50W (H⁺) 、 对甲苯磺酸 、 硫脲 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 甲醇 、 乙醇 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 7.08h， 生成 8,2'-anhydro-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

• Studies of nucleosides and nucleotides—LXI
  作者：M. Ikehara、Y. Ogiso、T. Morii

  DOI：10.1016/0040-4020(76)80019-1

  日期：1976.1

  8,2′ - Anhydro - 8 - mercapto - 9 - β - d - arabinofuranosyladenine, 8,3′ - anhydro - 8 - mercapto - 9 - β - d - xylofuranosyladenine and 8,5′ - 8 - mercaptoadenosine were oxidized either with N-bromosuccinimide, t-butyl hypochlorite or performic acid to their 8-sulfoxides. Configuration of sulfoxides were determined to be S in former two cases. In the case of 8,5′-cyclonucleoside, both S- and R-compounds

  用以下方法将8,2'-脱水-8-巯基-9-β-d-阿拉伯呋喃糖腺嘌呤，8,3'-脱水-8-巯基-9-β-d-木呋喃糖基腺嘌呤和8,5'-8-巯基腺苷氧化N-溴代琥珀酰亚胺，次氯酸叔丁酯或过甲酸变成它们的8-亚砜。在前两种情况下，亚砜的构型确定为S。在8，5'-环核苷的情况下，获得了S-和R-化合物。记录了这些亚砜的UV，NMR和CD光谱。
• Studies of nucleosides and nucleotides—XLVI
  作者：M. Ikehara、M. Kaneko、M. Sagai

  DOI：10.1016/0040-4020(70)80013-8

  日期：——

  Compounds IIa, b gave 8,5′-anhydronucleosides (IV a and b) on treatment with hydrogen sulfide in pyridine or aqueous sodium hydrogen sulfide in pyridine at −5–−15°. The structure of IV was confirmed by UV absorption, NMR and elemental analysis. CD and ORD measurements of IV showed large positive Cotton effects around absorption maxima. Acidic removal of the protecting group in IV gave 8,5′-anhydro-8-mercaptoadenosine

  从8-溴腺苷开始，合成了2'，3'-O-异亚丙基-（IIa）和2'，3'-O-乙氧基亚甲基-5'-O-甲苯磺酰基-8-溴腺苷（IIb）。通过在吡啶中的硫化氢或在吡啶中的硫化氢钠水溶液在5-1-15°下处理，化合物IIa，b得到8,5'-脱水核苷（IV a和b）。IV的结构通过UV吸收，NMR和元素分析确认。IV的CD和ORD测量显示，在最大吸收附近，棉花有很大的正效应。酸性除去IV中的保护基，得到8,5'-脱水-8-巯基腺苷（V），将其脱硫得到5'-脱氧水杨酸（VI）。
• 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）。
• Polynucleotides. 33. Synthesis and properties of the dinucleoside monophosphates containing adenine S-cyclonucleosides and adenosine. Factors determining the stability and handedness of the stacking conformation in a dinucleoside monophosphate
  作者：Seiichi Uesugi、Junichi Yano、Emi Yano、Morio Ikehara

  DOI：10.1021/ja00449a049

  日期：1977.3
• Syntheses of potential antimetabolites. XV. Syntheses of a sulfonate analog of adenosine 5'-phosphate and an alternative synthesis of 5',8-S-anhydroadenine nucleosides and 5'-deoxyspongoadenosine and its isomers
  作者：Yoshihisa Mizuno、Chisato Kaneko、Yuji Oikawa

  DOI：10.1021/jo00926a033

  日期：1974.5