N9-propargylguanine | 944450-55-9

• 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: N9-propargylguanine
• 英文别名: 2-amino-9-prop-2-ynyl-1H-purin-6-one
• CAS: 944450-55-9
• 化学式: C₈H₇N₅O
• 分子量: 189.176
• InChiKey: HPVCEJJSQGKZOK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  85.3
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N9-propargylguanine 在 copper(l) iodide 、 四(三苯基膦)钯 、 三乙胺 作用下， 以 N,N-二甲基乙酰胺 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 5′-O-(4,4′-dimethoxytrityl)-5-(3-(2-N-isobutyrylguanin-9-yl)-propyn-1-yl)-2′-deoxyuridine
  参考文献：
  名称：

  Double-Coding Nucleic Acids: Introduction of a Nucleobase Sequence in the Major Groove of the DNA Duplex Using Double-Headed Nucleotides

  摘要：

  A series of double-headed nucleosides were synthesized using the Sonogashira cross-coupling reaction. In the reactions, additional nucleobases (thymine, cytosine, adenine, or guanine) were attached to the 5-position of 2'-deoxyuridine or 2'-deoxycytidine through a propyne linker. The modified nucleosides were incorporated into oligonucleotides, and these were combined in different duplexes that were analyzed by thermal denaturation studies. All of the monomers were well tolerated in the DNA duplexes and induced only small changes in the thermal stability. Consecutive incorporations of the monomers led to increases in duplex stability owing to increased stacking interactions. The modified nucleotide monomers maintained the Watson-Crick base pair fidelity. Stable duplexes were observed with heavily modified oligonucleotides featuring 14 consecutive incorporations of different double-headed nucleotide monomers. Thus, modified duplexes with an array of nucleobases on the exterior of the duplex were designed. Molecular dynamics simulations demonstrated that the additional nucleobases could expose their Watson-Crick and/or Hoogsteen faces for recognition in the major groove. This presentation of nucleobases may find applications in providing molecular information without unwinding the duplex.

  DOI：

  10.1021/jo501151w
• 作为产物：
  描述：

  N2-Boc-9-(prop-2-ynyl)-6-chloro-9H-purin-2-ylamine 在 甲酸 作用下， 以 水 为溶剂， 反应 2.0h， 以95%的产率得到N9-propargylguanine
  参考文献：
  名称：

  Concise access to N9-mono-, N2-mono- and N2,N9-di-substituted guanines via efficient Mitsunobu reactions

  摘要：

  Guanine poses several problems to the synthetic chemist owing to its polyfunctional nature and poor solubility. Over the past few decades, synthetic guanines have found applications as anti-cancer and anti-viral agents. Coupled with the ever-growing interest in designer PNAs and G-quartets, simple and efficient synthetic routes to novel guanines would be of significant benefit. We herein report that, upon simple protection and/or activation step(s), the guanine precursor 2-amino-6-chloropurine is rendered an excellent substrate for Mitsunobu chemistry, furnishing, after subsequent hydrolytic dechlorination and appropriate deprotection step(s), the desired N9-mono-, N2-mono- or N2,N9-di-substituted guanines in excellent yields (>= 80%). Importantly, we demonstrate that N9-functionalization proceeds with very good N9/N7 regioselectivity and with complete inversion of stereochemistry. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.03.118

文献信息

• Peptide Nucleic Acid with Double Face: Homothymine–Homocytosine Bimodal Cα-PNA (<i>bm</i>-Cα-PNA) Forms a Double Duplex of the <i>bm</i>-PNA₂:DNA Triplex
  作者：Manoj Kumar Gupta、Bharath Raj Madhanagopal、Krishna N. Ganesh

  DOI：10.1021/acs.joc.0c02158

  日期：2021.1.1

  complementary DNAs dA8 and dG6 at neutral pH, bm-Cα-PNA 1 forms a higher order pentameric double duplex of a triplex composed of two bm-Cα-PNA-C5:dG5 duplexes built on a core (bm-Cα-PNA-T7)2:dA8 triplex. Circular dichroism studies showed that assembly can be achieved by either triplex first and duplex later or vice versa. Isothermal titration calorimetry data indicated that the assembly is driven by

  Cα-双峰肽核酸（bm - Cα- PNA）是具有两个面的PNA，被设计为PNA的同源物，其中标准PNA骨架中的每个氨基乙基甘氨酸（aeg）重复单元在Cα处通过带有一个三唑接头。这种具有混合序列的bm -Cα-PNA可通过同时与两个互补DNA结合而形成双链体，两个互补DNA分别与t-酰胺侧的碱基序列结合，而另一个与Cα侧链的碱基结合。bm -Cα-PNA的合成，在叔酰胺面上有高胸腺嘧啶（T 7）和高胞嘧啶（C 5通过三唑接头在Cα侧链上的固相合成是通过固相合成和整体点击反应实现的。在互补DNA DA的存在8和DG 6在中性pH下，BM -Cα-PNA 1所形成高阶一个五聚体组成的三链体的双双工2 BM -Cα-PNA-C 5：dG的5个构建在核心双链（BM -Cα-PNA-T 7）2：DA 8三层 圆二色性研究表明，组装可以通过首先进行三重结合，然后通过双面进行，反之亦然。等温滴定量热法数
• Guanine–copper coordination polymers: crystal analysis and application as thin film precursors
  作者：N. Nagapradeep、V. Venkatesh、S. K. Tripathi、Sandeep Verma

  DOI：10.1039/c3dt52415a

  日期：——

  Three copper-N9-modified guanine complexes are reported with structures ranging from a discrete trinuclear motif to a mixed-valence coordination polymer. These complexes were used as precursors for the deposition and growth of copper oxide thin films on Si(100), at two different annealing temperatures, by using a CVD technique. Subsequent resistivity measurements suggest the formation of conductive thin films, raising the possibility of using nucleobase-metal complexes as versatile thin film precursors.

  报告了三种铜-N9-修饰的鸟嘌呤络合物，其结构从离散的三核单元到混合价态的配位聚合物。这些络合物被用作前驱体，通过化学气相沉积（CVD）技术，在两种不同的退火温度下，在Si(100)上沉积和生长铜氧化物薄膜。随后的电阻率测量表明形成了导电薄膜，提出了将核苷酸金属络合物作为多功能薄膜前驱体的可能性。
• Synthesis of nucleobase-neomycin conjugates and evaluation of their DNA binding, cytotoxicities, and antibacterial properties
  作者：Siwen Wang、Mandeep Singh、Mingheng Ling、Danni Li、Krege M. Christison、Joan Lin-Cereghino、Geoff P. Lin-Cereghino、Liang Xue

  DOI：10.1007/s00044-018-2169-x

  日期：2018.5

  nucleobase and neomycin conjugates via click chemistry. All four conjugates stabilized a DNA oligonucleotide triplex in the thermal denaturation experiments monitored by UV. The guanine-neomycin conjugate (6b) showed a better triplex stabilization effect than neomycin. All the conjugates, as well as neomycin, exhibited no thermal stabilization effect on a human telomeric DNA G-quadruplex. These results

  已知新霉素优先结合A型核酸结构，包括三链DNA，DNA和RNA杂合体以及双链RNA。将DNA嵌入剂部分束缚到新霉素环III的C5”位置是一种通过协同作用开发靶向各种核酸二级结构的有效结合剂的实用方法。然而，展示该效果所需的插入部分的最小堆积表面仍不清楚。在目前的工作中，我们通过点击化学合成了四个核碱基和新霉素结合物。在紫外监测的热变性实验中，所有四种缀合物均稳定了DNA寡核苷酸三链体。鸟嘌呤-新霉素结合物（6b）显示出比新霉素更好的三链体稳定作用。所有缀合物以及新霉素对人端粒DNA G-四链体均无热稳定作用。这些结果表明结合的协同作用在很大程度上取决于缀合物的堆积部分的表面积。此外，将核碱基拴系在新霉素的C5”位置可增强新霉素对MCF-7和HeLa癌细胞的细胞毒性，但会降低新霉素对几种革兰氏阴性和革兰氏阳性细菌的抗菌作用。
• Customizable and Regioselective One‐Pot N−H Functionalization of DNA Nucleobases to Create a Library of Nucleobase Derivatives for Biomedical Applications
  作者：Djenisa H. A. Rocha、Carmen M. Machado、Vera Sousa、Cristiana F. V. Sousa、Vera L. M. Silva、Artur M. S. Silva、João Borges、João F. Mano

  DOI：10.1002/ejoc.202100786

  日期：2021.8.20

  synthetic procedures for producing a library of nucleobase derivatives enlisted with reactive functional groups for bioconjugation and cross-linking reactions with other biomolecules are reported. The nucleobase derivatives bearing either N-alkyl, N-propanenitrile, N-allyl or N-propargyl terminals are non-cytotoxic, denoting great promise for biomedical applications.

  一锅合成程序用于生产核碱基衍生物库，该库具有反应性官能团，用于与其他生物分子进行生物共轭和交联反应。带有N - 烷基、N - 丙腈、N - 烯丙基或N -炔丙基末端的核碱基衍生物是无细胞毒性的，在生物医学应用方面具有广阔的前景。
• Toward the Supramolecular Cyclodextrin Dimers Using Nucleobase Pairs
  作者：Christophe Len、Vanessa Legros、Florian Hamon、Bruno Violeau、Frédéric Turpin、Florence Djedaini-Pilard、Jérôme Désiré

  DOI：10.1055/s-0030-1258354

  日期：2011.1

  The synthesis of eleven new cyclodextrin derivatives having nucleobase moiety - thymin-1-yl, adenin-9-yl, and guanin-9-yl - is described. These two moieties are linked by different spacers, such as aminoethyl and 1,2,3-triazolyl group. Direct nucleophilic substitution and 1,3-dipolar cycloaddition were performed in good yields (13-73%) for some of the synthesized compounds.

  描述了十一种新型环糊精衍生物的合成，这些衍生物具有核苷碱基部分——胸腺嘧啶-1-基、腺嘌呤-9-基和鸟嘌呤-9-基。这两个部分通过不同的间隔体连接，例如氨基乙基和1,2,3-噁唑基。对于一些合成的化合物，直接亲核取代反应和1,3-偶极环加成反应均在良好的产率（13-73%）下完成。