1-<2-Bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-1-(pivaloyloxy)-β-D-arabinofuranosyl>uracil | 153959-63-8

• 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: 1-<2-Bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-1-(pivaloyloxy)-β-D-arabinofuranosyl>uracil
• 英文别名: 1-[2-bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-1-pivaloyloxy-β-D-arabinofuranosyl]uracil；[(2S,3S,4R,5R)-3-bromo-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-(2,4-dioxopyrimidin-1-yl)oxolan-2-yl] 2,2-dimethylpropanoate
• CAS: 153959-63-8
• 化学式: C₂₆H₄₇BrN₂O₇Si₂
• 分子量: 635.743
• InChiKey: NEFGMZXTUSSKLG-CQBMSCNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.31
• 重原子数：
  38
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  103
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-<2-Bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-1-(pivaloyloxy)-β-D-arabinofuranosyl>uracil 在 三(三甲基硅基)硅烷 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 0.33h， 以95%的产率得到2,2-Dimethyl-propionic acid (2S,3R,4R,5R)-4-(tert-butyl-dimethyl-silanyloxy)-5-(tert-butyl-dimethyl-silanyloxymethyl)-2-(2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl ester
  参考文献：
  名称：

  用（Me 3 Si）3 SiH进行核苷的自由基转化。通过酰氧基的1，2-迁移产生C-1'自由基

  摘要：

  在自由基条件下，三（三甲基甲硅烷基）硅烷可还原许多核苷底物。在一种情况下，已经观察到新型的β-（酰氧基）烷基自由基重排，其导致C-1'自由基种类的产生导致α-核糖核苷的立体选择性制备。估计了上述1,2-迁移的速率，并与先前报告的结果进行了比较。

  DOI：

  10.1016/00404-0399(50)1340-n
• 作为产物：
  描述：

  1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-2-bromo-D-erythro-pento-1-enofuranosyl]uracil 在 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 1.25h， 生成 1-<2-Bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-1-(pivaloyloxy)-β-D-arabinofuranosyl>uracil 、 1-[2-bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-1-pivaloyloxy-α-D-ribofuranosyl]uracil
  参考文献：
  名称：

  通过同步消除 2'-卤代-2'-脱氧-1'-新戊酰氧基尿嘧啶核苷的新戊酸合成 2'-卤代-1',2'-不饱和尿苷衍生物的替代方法：制备其 2' -C-支链核苷

  摘要：

  摘要 已开发出一种制备 2'-溴-(5b) 和 2'-碘-(5c) 1',2'-不饱和尿嘧啶核苷的替代方法。该方案基于从 2'-溴-(7a,b) 和 2'-碘-(9a,b) 1'-新戊酰氧基-2'-脱氧尿苷衍生物中同步消除新戊酸，这些衍生物衍生来自 3',5'-双-O-TBDMS-1',2'-不饱和尿苷 1 的卤代新戊酰氧基化。 化合物 5b 和 5c 被证明可作为相应的 2'-C-支链 1' 的通用合成子,2'-不饱和尿嘧啶核苷，通过钯催化的交叉偶联或卤素-锂交换反应。图形概要

  DOI：

  10.1080/15257770.2019.1641724

文献信息

• Generation of C-1′ radicals through a β-(acyloxy)alkyl rearrangement in modified purine and pyrimidine nucleosides
  作者：Thanasis Gimisis、Giuseppina Ialongo、Chryssostomos Chatgilialoglu

  DOI：10.1016/s0040-4020(97)10317-9

  日期：1998.1

  12 with tributyltin hydride generates indirectly C-1′ radicals through a β-(acyloxy)alkyl rearrangement. Rate constants for these rearrangements have been measured by using free-radical clock methodology and comparison of these data with previous reported results provides structural information about the nature of this important class of radicals.

  受保护的1'，2'-二氢-2'-脱氧腺苷的合成已通过结合对腺嘌呤氨基官能团的亚磷叉基保护进行了优化。这些不饱和腺苷已用作亲电子碘新戊酰氧基化的底物，导致在异头位置被修饰的新核苷。卤代戊二酸酯10、11和12与氢化三丁基锡的反应通过β-（酰氧基）烷基重排间接产生C-1'自由基。这些重排的速率常数已通过使用自由基时钟方法进行了测量，并将这些数据与先前报道的结果进行比较可提供有关这一重要基团性质的结构信息。
• Nucleophilic Addition of Benzenethiol to 1‘,2‘-Unsaturated Nucleosides:  1‘-<i>C</i>-Phenylthio-2‘-deoxynucleosides as Anomeric Radical Precursors
  作者：Hiroki Kumamoto、Miki Murasaki、Kazuhiro Haraguchi、Aki Anamura、Hiromichi Tanaka

  DOI：10.1021/jo0201934

  日期：2002.8.1

  The addition reaction of benzenethiol to the glycal portion of 1',2'-unsaturated uridine proceeds efficiently in the presence of Et3N. The mechanism involves nucleophilic attack of thiolate at the anomeric position in the rate-determining step, wherein conjugation between the nucleobase and the glycal portion is crucial. The derivative having a methyl group either at the 2'- or 6-position did not undergo this addition reaction, due to their sterically prohibited coplanarity. The 1',2'-unsaturated derivatives of thymine and adenine can also be used as substrates for this addition reaction. It was also shown that the resulting 1'-C-phenylthio-2'-deoxynucleosides serve as precursors for radical-mediated C-C bond formation at the anomeric position.
• Radical-initiated 1,2-acyloxy migration which generates a nucleoside anomeric radical
  作者：Yoshiharu Itoh、Kazuhiro Haraguchi、Hiromichi Tanaka、Kouichiro Matsumoto、Kazuo T. Nakamura、Ta-i Miyasaka

  DOI：10.1016/0040-4039(95)00718-r

  日期：1995.5

  Face-selectivity of bromo-pivaloyloxylation to 1'2'-unsaturated uridine can be altered by changing the 3'5'-O-protecting group. The resulting 2'-bromo-1'-pivaloyloxylated adduct, upon being reacted under radical conditions, undergoes 1,2-acyloxy migration to generate a nucleoside anomeric radical which was allowed to react with Bu(3)SnH or allyltributyltin. Factors governing stereochemistry and efficacy of this migration are also discussed.
• Divergent and Stereocontrolled Approach to the Synthesis of Uracil Nucleosides Branched at the Anomeric Position
  作者：Yoshiharu Itoh、Kazuhiro Haraguchi、Hiromichi Tanaka、Eisen Gen、Tadashi Miyasaka

  DOI：10.1021/jo00108a031

  日期：1995.2

  Electrophilic addition of NBS/pivalic acid (bromopivaloyloxylation) to 1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pent- 1-enofuranosyl]uracil (2), readily accessible from O-2,2'-anhydro-uridine, furnished 1-[2-bromo-3,5-bis-O-(tert-butyldimethyylsilyl)-2-deoxy-1-(pivaloyloxy)-beta-D-ara-binofuranosyl]uracil (7) stereoselectively. This compound (7), having a leaving group at the 1'-position as well as 2'-beta-Br that could exert anchimeric assistance, serves as versatile intermediate for the stereocontrolled synthesis of various types of 1'-C-branched derivatives through nucleophilic substitutions by the use of organosilicon and organoaluminum reagents. The whole sequence constitutes the first example of the conversion of a naturally-occurring nucleoside to the analogues branched at the anomeric position.
• Stereoselective Synthesis of 1'-C-Branched Uracil Nucleosides from Uridine
  作者：Kazuhiro Haraguchi、Yoshiharu Itoh、Hiromichi Tanaka、Tadashi Miyasaka

  DOI：10.1080/15257779508012398

  日期：1995.5.1

  Face-selective electrophilic addition (bromo-pivaloyloxylation) to 1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pent-1-enofuranosyl]uracil (1), when combined with nucleophilic substitution using organosilicon or organoaluminum reagents, provides a new and highly divergent C-C bond forming method at the anomeric position.