(5'R)-5',8-cyclo-2'-deoxyadenosine

• 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: (5'R)-5',8-cyclo-2'-deoxyadenosine
• 英文别名: 5',8-cyclo-2'-deoxyadenosine；(5'R)-cdAdo；(5'R)-cdA；(5'R)cdA；8,5'-Cyclo-2'-deoxyadenosine；(1R,11R,12S,13S)-7-amino-15-oxa-2,4,6,9-tetrazatetracyclo[10.2.1.02,10.03,8]pentadeca-3,5,7,9-tetraene-11,13-diol
• 化学式: C₁₀H₁₁N₅O₃
• 分子量: 249.229
• InChiKey: MBVGIEDXZGVICG-FXZMZVCPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.8
• 重原子数：
  18
• 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：
  119
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  8,5(S)-环-2-脱氧腺苷酸 在 水 作用下， 反应 35.0h， 生成 (5'R)-5',8-cyclo-2'-deoxyadenosine
  参考文献：
  名称：

  Solar one-way photoisomerisation of 5′,8-cyclo-2′-deoxyadenosine

  摘要：

  在阳光照射下，(5-S)-5-,8-环-2-脱氧腺苷2光异构化为(5-R)异构体1，这是当这些环嘌呤损伤在DNA中形成时更容易修复的损伤。

  DOI：

  10.1039/b718222h

文献信息

• Model Studies of DNA C5‘ Radicals. Selective Generation and Reactivity of 2‘-Deoxyadenosin-5‘-yl Radical
  作者：Chryssostomos Chatgilialoglu、Maurizio Guerra、Quinto G. Mulazzani

  DOI：10.1021/ja029374d

  日期：2003.4.1

  cyclization is 1.6 x 10(5) s(-1). On the basis of the theoretical findings, the cyclization step is highly stereospecific. The rate constants for the reactions of C5' and aminyl 3 radicals with different oxidants were determined by pulse radiolysis methods. The respective rate constants for the reaction of 2'-deoxyadenosin-5'-yl radical with dioxygen, Fe(CN)(6)(3)(-), and MV(2+) in water at ambient temperature

  水合电子 (e(aq)(-)) 与 8-bromo-2'-deoxyadenosine 的反应已通过辐射分解方法与产品研究相结合进行了研究，并通过 DFT-B3LYP 计算解决了计算问题。脉冲辐解显示该反应在大约 0.3 亩内完成，此时未检测到显着吸收。在 20 亩内形成的瞬态光谱在 300-500 nm 范围内具有吸光度（epsilon(max) 与 360 nm 处的 9600 M(-1) cm(-1) 一致），并且它被指定为芳香胺基3. 计算出的垂直跃迁 (TD-UB3LYP/6-311+G) 与实验观察非常吻合。自由基 3 通过以下反应序列获得：C-Br 键的单电子还原裂解产生 C8 自由基，从 C8 到 C5' 的快速自由基易位 位置，以及 C5' 基团在腺嘌呤部分的 C8,N7 双键上的分子内攻击。环化的速率常数为 1.6 x 10(5) s(-1)。根据理论发现，环化步骤具有
• The Fate of C5′ Radicals of Purine Nucleosides under Oxidative Conditions
  作者：Fabien Boussicault、Panagiotis Kaloudis、Clara Caminal、Quinto G. Mulazzani、Chryssostomos Chatgilialoglu

  DOI：10.1021/ja800763j

  日期：2008.7.1

  purine-substituted C5' radicals (i.e., 2'-deoxyadenosin-5'-yl, 2'-deoxyinosin-5'-yl, and 2'-deoxyguanosin-5'-yl) under oxidative conditions using gamma-radiolysis coupled with product studies. 2'-Deoxyadenosin-5'-yl and 2'-deoxyinosin-5'-yl radicals were selectively generated by the reaction of hydrated electrons (e(aq)(-)) with 8-bromo-2'-deoxyadenosine and 8-bromo-2'-deoxyinosine followed by a rapid radical translocation

  在有氧条件下，影响嘌呤部分 C5' 自由基反应性的因素不仅在 DNA 中是未知的，在简单的核苷中也是未知的。5',8-环嘌呤损伤是在与氧反应之前对嘌呤部分进行快速 C5' 自由基攻击的结果。溶液中分子氧的存在抑制了 DNA 修饰中这些众所周知的损伤。在这里，我们阐明了三个嘌呤取代的 C5' 自由基（即 2'-脱氧腺苷-5'-基、2'-脱氧肌苷-5'-基和 2'-脱氧鸟苷-5'-基）在氧化条件下的化学反应使用伽马辐射与产品研究相结合。2'-Deoxyadenosin-5'-yl 和 2'-deoxyinosin-5'-yl 自由基是通过水合电子 (e(aq)(-)) 与 8-bromo-2' 的反应选择性产生的 -deoxyadenosine 和 8-bromo-2'-deoxyinosine，然后是从 C8 到 C5' 位置的快速自由基易位。用 Fe(CN)6(3-) 捕获这两个 C5' 自由基，得到相应的水合
• C5‘-Adenosinyl Radical Cyclization. A Stereochemical Investigation
  作者：Maria Luisa Navacchia、Chryssostomos Chatgilialoglu、Pier Carlo Montevecchi

  DOI：10.1021/jo060197z

  日期：2006.6.1

  A variety of substituted 2'-deoxyadenosin-5'-yl radicals 3 were generated under different reaction conditions. Radicals 3 underwent intramolecular cyclization onto the C8-N7 double bond of the adenine moiety leading to aminyl radicals (5'S,8R)-4 and (5'R,8R)-4 and, eventually, to the corresponding cyclonucleosides 5 and 6. The effect of the solvent, the nature of the substituents, and the generation method of radicals 3 on the stereoselectivity of the C5'-radical cyclization have been considered. The observed increase of the (5'S)/(5'R) ratio by increasing the bulkiness of the R-1 group is explained in terms of steric repulsion between R-1 and the purine moiety which favors the C5'-endo conformation, whereas the effect of the water solvent in promoting the (5'R)-stereoselective cyclization is ascribed to intermolecular hydrogen bonding stabilizing the C5'-exo confomation.
• Oxidative damage to DNA constituents by iron-mediated Fenton reactions: the deoxyadenosine family
  作者：Rajagopal Chattopadhyaya、Bhaswati Goswami

  DOI：10.1080/07391102.2012.682206

  日期：2012.8.1

  The effect of exposing 2'-deoxyadenosine (dA), 5'-dAMP, 3'-dAMP, dApA, dA(pdA)(19), and poly(dA): oligo(dT) to iron/H2O2 in the presence and absence of ethanol or NADH has been studied. HPLC retention times, enzyme treatments, radiolabeled substrates, UV absorption spectra, and fast atom bombardment mass spectrometry (FABMS) have been used to distinguish 20 products arising from the reaction, of which 16 have been identified and four anomers proposed by comparison with earlier gamma radiation studies. The radical responsible for the reactions seems to be analogous to radiation-derived (OH)-O-center dot, has many products in common, but has some novel ones probably specific for Fenton-induced damage. Two new dimeric adducts arising from the generation of hydroxylamine at N7 and its subsequent condensation with two known sugar damage products, dR-adenine-N1-oxide, and two isomers of dR-FAPy arising from radical attacks at C4 and C5, may be considered novel in the present study. Unlike radiation-derived (OH)-O-center dot, the radical under study is difficult to eliminate due to its generation in the proximity of the substrate molecules. It is proposed that the iron binds to the phosphate group and generates the radical in its vicinity. Strand breaks in dA(pdA)(11) resulting from the Fenton reaction are of two types, spontaneous and alkali-labile. Duplex DNA is less sensitive to attack by this radical, as its various degradation products are a subset of those obtained with monomer substrates and only dR-FAPy production is relatively enhanced for poly (dA): oligo (dT) as compared to those from other substrates.
• Site-Specific Introduction of (5‘<i>S</i>)-5‘,8-Cyclo-2‘-deoxyadenosine into Oligodeoxyribonucleotides
  作者：Anthony Romieu、Didier Gasparutto、Didier Molko、Jean Cadet

  DOI：10.1021/jo980083q

  日期：1998.7.1