8-ethenyl-2',3',5'-tris-O-(tert-butyldimethylsilyl)adenosine | 132065-04-4

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷
• 英文名称: 8-ethenyl-2',3',5'-tris-O-(tert-butyldimethylsilyl)adenosine
• 英文别名: FEG118；9-[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-8-ethenylpurin-6-amine
• CAS: 132065-04-4
• 化学式: C₃₀H₅₇N₅O₄Si₃
• 分子量: 636.07
• InChiKey: ZBSIUBFWRAXCKU-ZCIWVVNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.75
• 重原子数：
  42
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  107
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  8-ethenyl-2',3',5'-tris-O-(tert-butyldimethylsilyl)adenosine 在 氟化铵 作用下， 以 甲醇 为溶剂， 以50%的产率得到(2R,3R,4S,5R)-2-(6-氨基-8-乙烯基嘌呤-9-基)-5-(羟基甲基)四氢呋喃-3,4-二醇
  参考文献：
  名称：

  Synthesis and cytotoxic activity of 6-vinyl- and 6-ethynyluridine and 8-vinyl- and 8-ethynyladenosine

  摘要：

  It is well-known that the introduction of vinyl and ethynyl moieties into nucleosides is of crucial importance for cytostatic, antiviral, or other biological activities. In this study 6- and 8-vinyl-and -ethynyluridine and -adenosine were prepared by a general procedure involving the palladium-catalyzed cross-coupling of trimethylsilylacetylene or vinyltributyltin. The introduction of a vinyl group at C-6 of uridine or an ethynyl group at C-8 of adenosine resulted in nucleoside derivatives showing cytostatic activity against several murine and/or human tumor cell lines. Interestingly, 8-vinyladenosine had pronounced selective inhibitory effects on human (Molt/4F and MT-4) versus murine (L1210 and FM3A) tumor cell lines.

  DOI：

  10.1021/jm00001a025
• 作为产物：
  描述：

  O^2'_,O3'_,O5'-tris-(tert-butyl-dimethyl-silanyl)-adenosine 在 四(三苯基膦)钯 碘 、 lithium diisopropyl amide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 生成 8-ethenyl-2',3',5'-tris-O-(tert-butyldimethylsilyl)adenosine
  参考文献：
  名称：

  钯催化腺苷2'-脱氧腺苷和2'，3'-脱氧腺苷核苷的C-8烯丙基化和乙烯基化

  摘要：

  通过O-TBDMS保护的8-碘衍生物，腺苷2'，脱氧腺苷，2'，3'-二脱氧腺苷与乙烯基三丁基锡或烯丙基三丁基锡在Pd（PPh 3）4催化下的偶联反应，得到相应的8-取代的核苷。优异的产量。

  DOI：

  10.1016/s0040-4039(00)97983-8

文献信息

• Simple Methodology for Heck Arylation at C-8 of Adenine Nucleosides
  作者：Pallavi Lagisetty、Li Zhang、Mahesh K. Lakshman

  DOI：10.1002/adsc.200700418

  日期：2008.3.7

  A simple method for the arylation of 8-vinyladenine nucleoside derivatives is reported. With a broad set of aryl iodides and bromides, the reaction is catalyzed by the simple combination palladium acetate/tris(o-tolyl)phosphine/triethylamine [Pd(OAc)2/(o-tol)3P/Et3N]. As expected, aryl chlorides are more difficult coupling partners but some undergo reactions with more exotic catalysts. Although trans-olefins

  报道了一种简单的8-乙烯基缩水嘌呤核苷衍生物芳基化的方法。对于广泛的芳基碘化物和溴化物，该反应由乙酸钯/三（邻甲苯基）膦/三乙胺[Pd（OAc）2 /（邻甲苯基）3 P / Et 3 N]的简单组合催化。不出所料，芳基氯化物是更困难的偶合伙伴，但有些会与更奇特的催化剂发生反应。尽管反式烯烃是主要产物，但在某些情况下可检测到少量的顺式异构体，并提出了其形成后芳基化的机理。最后，通过微妙的催化剂调节化学选择性氮可以在乙烯基部分存在下实现核苷的芳基化。
• Diversely C8-functionalized adenine nucleosides <i>via</i> their underexplored carboxaldehydes
  作者：Hari K. Akula、Suyeal Bae、Padmanava Pradhan、Lijia Yang、Barbara Zajc、Mahesh K. Lakshman

  DOI：10.1039/d1cc06686b

  日期：——

  underexploited for C8 modifications of these nucleosides. Only in situ formation of 8-formyladenosine is known and a single application of an N-benzoyl derivative has been reported. On the other hand, 8-formyl-2′-deoxyadenosine and its applications remain unknown. Herein, we report straightforward, scalable syntheses of both N-unprotected 8-formyladenine nucleoside derivatives, and demonstrate broad diversification

  腺苷和 2'-脱氧腺苷的潜在用途广泛的N-未保护 8-甲酰基衍生物在这些核苷的 C8 修饰方面开发不足。只有8-甲酰腺苷的原位形成是已知的，并且已经报道了N-苯甲酰基衍生物的单一应用。另一方面，8-甲酰基-2'-脱氧腺苷及其应用仍然未知。在这里，我们报告了两种N-未保护的 8-甲酰腺嘌呤核苷衍生物的直接、可扩展的合成，并通过羟甲基化、叠氮化、CuAAC 连接、还原胺化以及改性 Julia 和霍纳的烯化和氟烯化证明了 C8 位的广泛多样化–Wadsworth–Emmons 试剂。
• Synthesis of 8-vinyladenosine 5′-di- and 5′-triphosphate: evaluation of the diphosphate compound on ribonucleotide reductase
  作者：Pascal Lang、Catherine Gerez、Denis Tritsch、Marc Fontecave、Jean-François Biellmann、Alain Burger

  DOI：10.1016/s0040-4020(03)01151-7

  日期：2003.9

  The synthesis of 5'-di- and 5'-triphosphate of 8-vinyladenosine to be tested on ribonucleotide reductases requires the modification of known methods. The phosphate group was introduced by treatment with an in situ generated chlorophosphite. Protection of the 2',3' diol with acetyl groups suppressed depurination during acid removal of the phosphotriester protecting groups. The di- and triphosphate compounds were obtained by treatment of the activated adenylic acid with phosphate or pyrophosphate anions followed by removal of the acetate protecting groups. Preliminary studies were conducted on Escherichia coli ribonucleotide reductase and have shown that the diphosphate compound is efficiently reduced. (C) 2003 Elsevier Ltd. All rights reserved.
• MORIARTY, ROBERT M.;EPA, W. RUWAN;K. , AWASTHI ALOK, TETRAHEDRON LETT., 31,(1990) N1, C. 5877-5880
  作者：MORIARTY, ROBERT M.、EPA, W. RUWAN、K. , AWASTHI ALOK

  DOI：——

  日期：——
• Palladium catalysed C-8 allylation and vinylation of adenosine 2′-deoxyadenosine and 2′,3′-dideoxyadenosine nucleosides
  作者：Robert M. Moriarty、W.Ruwan Epa、Alok K. Awasthi

  DOI：10.1016/s0040-4039(00)97983-8

  日期：1990.1

  Using a coupling reaction between 8-iodo derivatives of O-TBDMS protected adenosine, 2′deoxyadenosine, 2′,3′-dideoxyadenosine and either vinyltributyltin or allyltributyltin with Pd(PPh3)4 catalysis, the corresponding 8-substituted nucleosides were obtained in excellent yields.

  通过O-TBDMS保护的8-碘衍生物，腺苷2'，脱氧腺苷，2'，3'-二脱氧腺苷与乙烯基三丁基锡或烯丙基三丁基锡在Pd（PPh 3）4催化下的偶联反应，得到相应的8-取代的核苷。优异的产量。