2',3',5'-tris-O-tert-butyldimethylsilyl-8-iodoadenosine | 132087-98-0

• 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: 2',3',5'-tris-O-tert-butyldimethylsilyl-8-iodoadenosine
• 英文别名: 2',3',5'-tri-O-tert-butyldimethylsilyl-8-iodoadenosine；9-[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-8-iodopurin-6-amine
• CAS: 132087-98-0
• 化学式: C₂₈H₅₄IN₅O₄Si₃
• 分子量: 735.929
• InChiKey: YCQWHAHGYUOHRV-UMCMBGNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.71
• 重原子数：
  41
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  2',3',5'-tris-O-tert-butyldimethylsilyl-8-iodoadenosine 在 吡啶 、 四丁基氟化铵 、 水 、 二氯-三(2,4,6-三溴苯氧基)膦烷 、 三氟乙酸 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 Phosphoric acid (2R,3S,4R,5R)-5-(6-amino-8-iodo-purin-9-yl)-3,4-dihydroxy-tetrahydro-furan-2-ylmethyl ester di-tert-butyl ester
  参考文献：
  名称：

  Synthesis of 8-vinyladenosine 5′-di- and 5′-triphosphate: evaluation of the diphosphate compound on ribonucleotide reductase

  摘要：

  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.

  DOI：

  10.1016/s0040-4020(03)01151-7
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正庚烷 、 二氯甲烷 、 乙基苯 、 N,N-二甲基甲酰胺 为溶剂， 反应 8.5h， 生成 2',3',5'-tris-O-tert-butyldimethylsilyl-8-iodoadenosine
  参考文献：
  名称：

  C8修饰的腺苷中仲羟基反应性的变化–甲硅烷基化的经验教训

  摘要：

  特定位点修饰的寡核苷酸的合成已成为RNA结构和功能研究的主要工具。报告者基团或特定的功能实体必须连接在低聚物的预定位点。一种有吸引力的策略是掺入适当功能化的结构单元，以允许所需部分的合成后缀合。合成了C8-炔基修饰的腺苷衍生物，从而恢复了嘌呤核碱基碘化的古老合成途径。C8-炔基修饰的腺苷的甲硅烷基化显示两个仲糖羟基具有3'- O的出乎意料的选择性-优先形成的异构体。保护方案的优化导致了一条新的经济途径，可通往所需的C8-炔基化构件并将其并入RNA。

  DOI：

  10.3762/bjoc.16.234

文献信息

• Halogen–deuterium exchange reaction mediated by tributyltin hydride using THF-d8 as the deuterium source
  作者：Tomonobu Mutsumi、Hiroki Iwata、Kazuo Maruhashi、Yasunari Monguchi、Hironao Sajiki

  DOI：10.1016/j.tet.2010.12.007

  日期：2011.2

  A regioselective deuteration method for a wide variety of aromatic compounds using the halogen–deuterium exchange reaction initiated by Bu3SnH using THF-d8 as the deuterium source was developed.

  开发了一种区域选择性氘化方法，该方法通过使用THF- d 8作为氘源，通过Bu 3 SnH引发的卤素-氘交换反应，对多种芳香族化合物进行区域选择性氘化。
• 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。
• 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。
• Alternative I-D Exchange Reaction on Pyrimidine and Purine Nuclei Mediated by Tributyltin Hydride Using THF-<i>d</i> ₈ as a Deuterium Source
  作者：Tomonobu Mutsumi、Kazuo Maruhashi、Yasunari Monguchi、Hironao Sajiki

  DOI：10.1055/s-0028-1083548

  日期：——

  A method for the regioselective deuteration of pyrimidine and purine rings mediated by BU 3 SnH using THF-d 8 as a deuterium source on the basis of a radical reaction was developed.

  开发了一种基于自由基反应使用 THF-d 8 作为氘源的 BU 3 SnH 介导的嘧啶和嘌呤环的区域选择性氘化方法。
• Synthesis of Purinecarbonitriles by Pd(0)-Catalysed Coupling of Halopurines with Zinc Cyanide.
  作者：Lise-Lotte Gundersen、Klaus Bechgaard、Klaus Bechgaard、Jon Songstad、Markku Leskelä、Mika Polamo、Muhammed Nour Homsi、Frank K. H. Kuske、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-0058

  日期：——

  Pd(0)-catalysed coupling of halopurines with zinc cyanide allows the smooth introduction of the cyano group into the purine 2-, 6- and 8-positions. Pronounced ligand effects were observed, and tetrakis(tri-2-furylphosphine)palladium(0) was found to be the catalyst of choice in reactions where tetrakis(triphenylphosphine)palladium(0) failed.