2',3',5'-tris-(O-tert-butyldimethylsilyl)-8-oxo-7,8-dihydroguanosine | 160622-93-5

• 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-oxo-7,8-dihydroguanosine
• 英文别名: 2',3',5'-tris((tert-butyldimethylsilyl)oxy)-8-oxo-7,8-dihydroguanosine；2',3',5'-tri<(tert-butyldimethylsilyl)oxy>-7,8-dihydro-8-oxoguanosine；tri-tert-butyldimethylsilyl 8-oxo-7,8-dihydroguanine；8-oxoguanosine；2-amino-9-[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-1,7-dihydropurine-6,8-dione
• CAS: 160622-93-5
• 化学式: C₂₈H₅₅N₅O₆Si₃
• 分子量: 642.031
• InChiKey: CYWJVOCXRVZXGB-ZDXOVATRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  42
• 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：
  137
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2',3',5'-tris-(O-tert-butyldimethylsilyl)-8-oxo-7,8-dihydroguanosine 在 氧气 、 tetraphenylporphyrin 作用下， 以 丙酮 为溶剂， 反应 0.5h， 生成 2-Amino-9-[(2R,3R,4R,5R)-3,4-bis-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-tetrahydro-furan-2-yl]-5-hydroperoxy-5,7-dihydro-9H-purine-6,8-dione
  参考文献：
  名称：

  Characterization of 5-Hydroxy-8-oxo-7,8-dihydroguanosine in the Photosensitized Oxidation of 8-Oxo-7,8-dihydroguanosine and Its Rearrangement to Spiroiminodihydantoin

  摘要：

  The photosensitized oxidation of 2',3',5'-tris-(O-tert-butyldimethylsilyl)-8-oxo-7,8-dihydroguansine (8-oxoG) with singlet oxygen was studied by low-temperature NMR. A stable intermediate was characterized at -60 degreesC by C-13, 2D NMR HMBC spectra, and chemical shifts calculated by hybrid Hallree-Fock density functional theory which agreed with the structure 5-hydroperoxy-8-oxo-7,8-dihydroquanosine. Reduction of this intermediate at low temperature afforded the corresponding alcohol, the long-postulated 5-hydroxy8-oxo-7,8-dihydroguanosine, the last intermediate in the formation of spiroiminodihydantoin. Upon warming to room temperature, this alcohol rearranges to form the spiroiminodihydantoin in good yield within 2 h.

  DOI：

  10.1021/ja030678p
• 作为产物：
  描述：

  鸟苷 在 咪唑 、 2,9,16,23-tetra-t-butyl-29H,31H-phthalocyanine 、 氧气 、 焦磷酸硫胺素 作用下， 以 二氯甲烷-D2 、 N,N-二甲基甲酰胺 为溶剂， 反应 62.0h， 生成 2',3',5'-tris-(O-tert-butyldimethylsilyl)-8-oxo-7,8-dihydroguanosine
  参考文献：
  名称：

  鸟苷衍生物的低温光敏氧化和​​咪唑开环产物的形成

  摘要：

  制备了有机可溶性鸟苷衍生物 2',3',5'-O-（叔丁基二甲基甲硅烷基）鸟苷 (1)，并在多种溶剂中在不同温度下对其进行了光敏氧化。单线态氧是负责该反应的活性氧化剂。即使在 -78 摄氏度，低温 NMR 也未检测到内过氧化物和二氧杂环丁烷中间体。具有氧化咪唑环的产物 (A) 是室温下唯一检测到的主要产物；该化合物可以通过低温柱色谱分离，并通过（1）H和（13）C和质谱进行表征。CO(2) 是另一个主要产品。少量相应的8-oxo-7，

  DOI：

  10.1021/ja011696e

文献信息

• Reactivity toward Singlet Oxygen of a 7,8-Dihydro-8-oxoguanosine ("8-Hydroxyguanosine") Formed by Photooxidation of a Guanosine Derivative
  作者：Chimin Sheu、Christopher S. Foote

  DOI：10.1021/ja00129a004

  日期：1995.6

  Total quenching (k(r) + k(q)) and chemical reaction rates (k(r)) for the removal of singlet oxygen by 2,3',5'-tris((tert-butyldimethylsilyl)oxy)guanos (1) and its oxidation product, 2',3',5'-tris((tert-butyldimethylsilyl)oxy)-7,8-dihydro-8-oxoguanosine (2), were determined by the time-resolved infrared luminescence technique and competition experiments, respectively. Compound 2 is two orders of magnitude more reactive with singlet oxygen than 1. A mechanism for the formation of 2 from 1 with singlet oxygen is proposed.
• Synthesis of 5-N-tert-butylaminoxylcytidine and EPR studies on its base pairing properties
  作者：Mariko Aso、Yasuhiro Matsui、Bo Yang、Midori Sasagaki、Daiki Okado、Kazuteru Usui、Noboru Koga、Hiroshi Suemune

  DOI：10.1016/j.tet.2015.05.080

  日期：2015.8

  5-N-tert-Butylaminoxylcytidine was synthesized as a new spin-labelled cytidine to detect guanosine by EPR spectroscopy. Metal-halogen exchange reaction of TBS-protected N-benzoyl-5-iodocytidine followed by a reaction with 2-methyl-2-nitrosopropane afforded 5-N-tert-butylhydroxylaminocytidine with considerable affinity for guanosine and its oxidation gave 5-N-tert-butylaminoxylcytidine. Changes in EPR parameters monitored its selective base pairing with guanosine derivatives and the formation of a 2:2 complex with 8-oxoguanosine. (C) 2015 Elsevier Ltd. All rights reserved.
• Photosensitized Oxygenation of a 7,8-Dihydro-8-oxoguanosine Derivative. Formation of Dioxetane and Hydroperoxide Intermediates
  作者：Chimin Sheu、Christopher S. Foote

  DOI：10.1021/ja00106a054

  日期：1995.1

  Low-temperature NMR studies of the dye-sensitized photooxygenation of an 8-oxoguanosine derivative provide direct evidence for dioxetanes as primary intermediates and their unprecedented rearrangement to hydroperoxides. These dioxetanes and hydroperoxides are stable only at low temperatures. Upon warming, they rearrange to a variety of products.
• Low-Temperature Photosensitized Oxidation of a Guanosine Derivative and Formation of an Imidazole Ring-Opened Product
  作者：Chimin Sheu、Ping Kang、Saeed Khan、Christopher S. Foote

  DOI：10.1021/ja011696e

  日期：2002.4.1

  photooxidation and was shown to be intermediate in the formation of two products of extensive degradation, C and D. Reaction of 1 with the singlet oxygen analogues 4-methyl-1,2,4-triazoline-3,5-dione (MTAD) and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) gave products consistent with a proposed mechanism involving the rearrangement of an initially formed endoperoxide to give A and B from reaction of 1 with singlet

  制备了有机可溶性鸟苷衍生物 2',3',5'-O-（叔丁基二甲基甲硅烷基）鸟苷 (1)，并在多种溶剂中在不同温度下对其进行了光敏氧化。单线态氧是负责该反应的活性氧化剂。即使在 -78 摄氏度，低温 NMR 也未检测到内过氧化物和二氧杂环丁烷中间体。具有氧化咪唑环的产物 (A) 是室温下唯一检测到的主要产物；该化合物可以通过低温柱色谱分离，并通过（1）H和（13）C和质谱进行表征。CO(2) 是另一个主要产品。少量相应的8-oxo-7，
• Characterization of 5-Hydroxy-8-oxo-7,8-dihydroguanosine in the Photosensitized Oxidation of 8-Oxo-7,8-dihydroguanosine and Its Rearrangement to Spiroiminodihydantoin
  作者：Jeremy E. B. McCallum、Corrie Y. Kuniyoshi、Christopher S. Foote

  DOI：10.1021/ja030678p

  日期：2004.12.1

  The photosensitized oxidation of 2',3',5'-tris-(O-tert-butyldimethylsilyl)-8-oxo-7,8-dihydroguansine (8-oxoG) with singlet oxygen was studied by low-temperature NMR. A stable intermediate was characterized at -60 degreesC by C-13, 2D NMR HMBC spectra, and chemical shifts calculated by hybrid Hallree-Fock density functional theory which agreed with the structure 5-hydroperoxy-8-oxo-7,8-dihydroquanosine. Reduction of this intermediate at low temperature afforded the corresponding alcohol, the long-postulated 5-hydroxy8-oxo-7,8-dihydroguanosine, the last intermediate in the formation of spiroiminodihydantoin. Upon warming to room temperature, this alcohol rearranges to form the spiroiminodihydantoin in good yield within 2 h.