5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylidene-5-bromouridine | 869880-87-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylidene-5-bromouridine
• 英文别名: 5-fluoro-6-amido-UMP；1-[(3aR,4R,6R,6aR)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-5-bromopyrimidine-2,4-dione
• CAS: 869880-87-5
• 化学式: C₁₈H₂₉BrN₂O₆Si
• 分子量: 477.428
• InChiKey: JXOHZASGISIFIC-RGCMKSIDSA-N

物化性质

• 密度：
  1.316±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.74
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  86.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylidene-5-bromouridine 在 吡啶 、 水 、 三氟乙酸 、 三氯氧磷 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 32.0h， 生成 6-cyanouridine 5'-monophosphate
  参考文献：
  名称：

  WO2008/83465

  摘要：

  公开号：
• 作为产物：
  描述：

  5'-O-(t-butyldimethylsilyl)-2',3'-O-isopropylideneuridine 在 1,3-二溴-5,5-二甲基海因 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以98%的产率得到5'-O-(tert-butyldimethylsilyl)-2',3'-O-isopropylidene-5-bromouridine
  参考文献：
  名称：

  Bromination at C-5 of pyrimidine and C-8 of purine nucleosides with 1,3-dibromo-5,5-dimethylhydantoin

  摘要：

  Treatment of the protected and unprotected nucleosides with 1,3-dibromo-5,5-dimethylhydantoin in aprotic solvents such as CH2Cl2, CH3CN, or DMF effected smooth bromination of uridine and cytidine derivatives at C-5 of pyrimidine rings as well as adenosine and guanosine derivatives at C-8 of purine rings. Addition of Lewis acids such as trimethylsilyl trifluoromethanesulfonate enhanced the efficiency of bromination. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.04.081

文献信息

• Practical synthesis of 6-aryluridines via palladium(II) acetate catalyzed Suzuki–Miyaura cross-coupling reaction
  作者：Yu-Chiao Shih、Tun-Cheng Chien

  DOI：10.1016/j.tet.2011.03.051

  日期：2011.5

  Sugar-protected 6-halouridine derivatives underwent Suzuki–Miyaura cross-coupling reactions with arylboronic acids in the presence of palladium(II) acetate as a catalyst, triphenylphosphine as a ligand, and sodium carbonate as a base. This methodology is applicable to both the C5- and C6-position of uridine and provides a direct access for versatile uridine derivatives.

  在乙酸钯（II）作为催化剂，三苯基膦作为配体和碳酸钠作为碱的存在下，糖保护的6-卤代吡啶衍生物与芳基硼酸进行了Suzuki-Miyaura交叉偶联反应。该方法学适用于尿苷的C5和C6位置，并为通用尿苷衍生物提供了直接途径。
• An Unprecedented Twist to ODCase Catalytic Activity
  作者：Masahiro Fujihashi、Angelica M. Bello、Ewa Poduch、Lianhu Wei、Subhash C. Annedi、Emil F. Pai、Lakshmi P. Kotra

  DOI：10.1021/ja054865u

  日期：2005.11.1

  Orotidine-5'-monophosphate decarboxylase (ODCase) has evolved to catalyze a decarboxylation reaction, most probably via a carbanion species at the C6 position of orotidine-5'-monophosphate. We reveal an unusual biochemical pathway of conversion of 6-cyano-uridine-5'-monophosphate by ODCase to barbiturate-5'-monophosphate via perhaps an electrophilic center at the C6 position, leading to inhibition

  Orotidine-5'-monophosphate decarboxylase (ODCase) 已经进化为催化脱羧反应，最有可能是通过 orotidine-5'-monophosphate 的 C6 位置的碳负离子物种。我们揭示了 ODCase 将 6-cyano-uridine-5'-monophosphate 转化为 barbiturate-5'-monophosphate 的一种不寻常的生化途径，可能通过 C6 位置的亲电子中心，导致抑制。ODCase 的这种潜力在设计新型抑制剂时非常有用。
• Lys314 is a Nucleophile in Non-Classical Reactions of Orotidine-5′-Monophosphate Decarboxylase
  作者：Daniel Heinrich、Ulf Diederichsen、Markus Georg Rudolph

  DOI：10.1002/chem.200900397

  日期：2009.7.6

  Molecular versatility: Unusual reactivities such as hydrolysis, nucleophilic aromatic substitution, and addition reactions of human orotidine‐5′‐monophosphate decarboxylase are explained by crystal structures and involve a nucleophilic lysine residue that normally is expected to act solely as a general base (RP=phosphoribosyl, R=CO2H, CN, acetyl, N3, I; R′=OH, SH, acetyl, hydroxymethyl).

  分子多功能性：异常的反应性，例如水解，亲核芳香族取代以及人orotidine-5'-单磷酸脱羧酶的加成反应，都由晶体结构解释，并且涉及亲核赖氨酸残基，通常预期其仅作为一般碱基起作用（RP =磷酸核糖基，R ＝ CO 2 H，CN，乙酰基，N 3，I； R′＝ OH，SH，乙酰基，羟甲基）。
• WO2007/38859
  申请人：——

  公开号：——

  公开（公告）日：——
• Synthesis of 6-Alkyluridines from 6-Cyanouridine via Zinc(II) Chloride-Catalyzed Nucleophilic Substitution with Alkyl Grignard Reagents
  作者：Yu-Chiao Shih、Ya-Ying Yang、Chun-Chi Lin、Tun-Cheng Chien

  DOI：10.1021/jo400364p

  日期：2013.4.19

  6-Cyanouracil derivatives underwent a direct nucleophilic substitution reaction with alkyl Grignard reagents in the presence of zinc(II) chloride as a catalyst to form the corresponding 6-alkyluracils. This methodology is applicable to sugar-protected 6-cyanouridine and 6-cyano-2'-deoxyuridine without the protection at the N-3-imide and provides a facile and general access to versatile 6-alkyluracil and 6-alkyluridine derivatives.