5-hydroxymethylene-3',5'-di-O-acetyl-2'-desoxyuridine | 139675-41-5

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: 5-hydroxymethylene-3',5'-di-O-acetyl-2'-desoxyuridine
• 英文别名: 3',5'-di-O-acetyl-5-hydroxymethyl-2'-deoxyuridine；5-hydroxymethyl-3',5'-di-O-acetyl-2'-deoxyuridine；5-hydroxymethyl-5',3'-di-O-acetyl-2'-deoxyuridine；O^3',O^5'-diacetyl-α-hydroxy-thymidine；2'-Deoxy-3',5'-diacetyl-5-(Hydroxymethyl)-uridin；[(2R,3S,5R)-3-acetyloxy-5-[5-(hydroxymethyl)-2,4-dioxopyrimidin-1-yl]oxolan-2-yl]methyl acetate
• CAS: 139675-41-5
• 化学式: C₁₄H₁₈N₂O₈
• 分子量: 342.306
• InChiKey: NVCVGORCSZSWMV-QJPTWQEYSA-N

物化性质

• 密度：
  1.45±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  132
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5-hydroxymethylene-3',5'-di-O-acetyl-2'-desoxyuridine 在 三甲基氯硅烷 、 sodium azide 作用下， 以 1,4-二氧六环 、 N,N-二甲基甲酰胺 为溶剂， 以83 %的产率得到5-azidomethyl-3',5',di-O-acetylthymidine
  参考文献：
  名称：

  5-羟甲基嘧啶核苷的制备：重新研究

  摘要：

  重新研究了目前用于将 5-羟​​甲基部分引入到基于嘧啶的脱氧核苷上的不同方法。胸苷甲基的氧化随后所得甲酰基的还原使得能够以简单的方式并以良好的产率获得受保护的5-羟甲基-2'-脱氧尿苷。给出了相关构建模块合成的应用示例。

  DOI：

  10.1002/ejoc.202300298
• 作为产物：
  描述：

  3',5'-di-O-acetyl-2'-deoxy-5-formyluridine 在 sodium tetrahydroborate 、 cerium(III) chloride heptahydrate 作用下， 以 甲醇 为溶剂， 以92 %的产率得到5-hydroxymethylene-3',5'-di-O-acetyl-2'-desoxyuridine
  参考文献：
  名称：

  5-羟甲基嘧啶核苷的制备：重新研究

  摘要：

  重新研究了目前用于将 5-羟​​甲基部分引入到基于嘧啶的脱氧核苷上的不同方法。胸苷甲基的氧化随后所得甲酰基的还原使得能够以简单的方式并以良好的产率获得受保护的5-羟甲基-2'-脱氧尿苷。给出了相关构建模块合成的应用示例。

  DOI：

  10.1002/ejoc.202300298

文献信息

• Selective reduction of aldehydes and ketones to alcohols with ammonia borane in neat water
  作者：Lei Shi、Yingying Liu、Qingfeng Liu、Bin Wei、Guisheng Zhang

  DOI：10.1039/c2gc00006g

  日期：——

  Chemoselective reduction of various carbonyl compounds to alcohols with ammonia borane (AB), a nontoxic, environmentally benign, and easily handled reagent, in neat water was achieved in quantitative conversions and high isolated yields. Interestingly, α- and β-keto esters were selectively reduced to corresponding hydroxyl esters by AB, while diols were obtained when sodium borohydride was used as

  化学选择性 减少 各种 羰基化合物 到 酒类 纯净的氨硼烷（AB），一种无毒，对环境无害且易于处理的试剂 水通过定量转化和高分离收率实现了这一目标。有趣的是，α-和β-酮基酯类 被AB选择性还原为相应的羟基酯，而 二醇类 是在什么时候获得的 硼氢化钠 被用作 还原剂。该方法还与多种碱不稳定的保护基的存在兼容，例如甲苯磺酰， 乙酰基， 苯甲酰基，酯基和酸不稳定的保护基，例如 三苯甲基 和TBDMS基团，以及其他基团，例如不饱和双键， 硝基的和氰基。最后，一公斤的反应苯甲酰甲酸酯 与AB进行了 水 并给了 扁桃酸甲酯 收率达94％。
• Synthesis and Antiviral Activity of New 5-Substituted 2′-Deoxyuridine Derivatives
  作者：A. V. Ivanov、A. R. Simonyan、E. F. Belanov、L. A. Aleksandrova

  DOI：10.1007/s11171-005-0076-7

  日期：2005.11

  New 5-azole- and 5-oxime-substituted analogues of 2′-deoxyuridine are synthesized. The analogues with azole ring manifest low toxicities and antiherpetic activities on Vero cell culture, the imidazole derivative being the most active. The inhibitory effects of oximes of 5-formyl-deoxyuridine are comparable with those of the azole-containing nucleoside analogues, although their cytotoxicities are found

  合成了 2'-脱氧尿苷的新 5-唑和 5-肟取代类似物。具有唑环的类似物对 Vero 细胞培养物表现出低毒性和抗疱疹活性，其中咪唑衍生物最为活跃。5-甲酰基-脱氧尿苷肟的抑制作用与含唑核苷类似物的抑制作用相当，但发现它们的细胞毒性更高；5-甲酰基脱氧尿苷的肟特别有毒。合成的核苷类似物对感染各种痘病毒变体的细胞培养物没有表现出明显的活性。
• Oxidative Damage of Thymidines by the Atmospheric Free-Radical Oxidant NO3•
  作者：Uta Wille、Catrin Goeschen

  DOI：10.1071/ch11102

  日期：——

  Analysis of the products formed in the reaction of nitrate radicals, NO3 •, with the N- and O-methylated and acetylated thymidines 1a and 1b revealed, for the first time, insight regarding how this important atmospheric free-radical oxidant can cause irreversible damage to DNA building blocks. Mechanistic studies indicated that the initial reaction step likely proceeds via NO3 • induced electron transfer at the pyrimidine ring, followed by deprotonation of the methyl group at C5. The oxidation ultimately leads to formation of nitrates 2, aldehydes 4 and, in the case of high [NO3 •], also to carboxylic acids 5. In addition to this, through a very minor pathway, loss of the methyl group at C5 also occurred to give the respective 2′-deoxyuridines 6. The nitrates 2 are highly labile compounds that undergo rapid hydrolysis during work-up and purification of the reaction mixtures, which could lead to serious misinterpretation of the experimental findings and reaction mechanism. Products resulting from NO3 • addition to the C5=C6 double bond in the pyrimidine ring were not observed. Also, no reaction of NO3 • with the 2′-deoxyribose moiety was detected.

  对硝酸根（NO3 -与 N-、O-甲基化和乙酰化胸腺嘧啶 1a 和 1b 反应形成的产物进行分析，首次揭示了这种重要的大气自由基氧化剂是如何对 DNA 构建模块造成不可逆损伤的。机理研究表明，最初的反应步骤可能是通过 - 诱导嘧啶环上的电子转移，然后 C5 上的甲基发生去质子化反应。氧化作用最终会形成硝酸盐 2 和醛类 4，在[ -]含量较高的情况下，还会形成羧基。 -]的情况下，还会产生羧酸 5。除此以外，通过一个非常次要的途径，C5 上的甲基也会发生脱失，从而生成相应的 2′-脱氧尿苷 6。硝酸盐 2 是高度易变的化合物，在反应混合物的加工和纯化过程中会发生快速水解，这可能导致对实验结果和反应机理的严重误解。 - 加到嘧啶环的 C5=C6 双键上所产生的产物未被观察到。此外，也没有观察到 - 与 2′-脱氧核糖分子的反应。
• STACKING NUCLEIC ACID AND METHODS FOR USE THEREOF
  申请人：Schneider Uffe Vest

  公开号：US20140065676A1

  公开（公告）日：2014-03-06

  The present invention provides a novel modified oligonucleotide monomer useful in molecular biological techniques such as capture and/or detection of nucleic acids, amplification of nucleic acids and sequencing of nucleic acids. The modified oligonucleotide monomer comprises an intercalator that can intercalate into an antiparallel duplex from the major groove.

  本发明提供了一种新型的修饰寡核苷酸单体，在分子生物学技术中具有捕获和/或检测核酸、核酸扩增和核酸测序等方面的应用。该修饰寡核苷酸单体包括一种可以插入到反平行双链的主沟槽中的插入剂。
• Three new double-headed nucleotides with additional nucleobases connected to C-5 of pyrimidines; synthesis, duplex and triplex studies
  作者：Pawan Kumar、Pawan K. Sharma、Jonas Hansen、Lukas Jedinak、Charlotte Reslow-Jacobsen、Mick Hornum、Poul Nielsen

  DOI：10.1016/j.bmc.2015.12.043

  日期：2016.2

  In the search for double-coding DNA-systems, three new pyrimidine nucleosides, each coded with an additional nucleobase anchored to the major groove face, are synthesized. Two of these building blocks carry a thymine at the 5-position of 20-deoxyuridine through a methylene linker and a triazolomethylene linker, respectively. The third building block carries an adenine at the 6-position of pyrrolo-20-deoxycytidine through a methylene linker. These double-headed nucleosides are introduced into oligonucleotides and their effects on the thermal stabilities of duplexes are studied. All studied double-headed nucleotide monomers reduce the thermal stability of the modified duplexes, which is partially compensated by using consecutive incorporations of the modified monomers or by flanking the new double-headed analogs with members of our former series containing propyne linkers. Also their potential in triplex-forming oligonucleotides is studied for two of the new double-headed nucleotides as well as the series of analogs with propyne linkers. The most stable triplexes are obtained with single incorporations of additional pyrimidine nucleobases connected via the propyne linker. (c) 2016 Elsevier Ltd. All rights reserved.