1-<1-C-Acetonyl-2-bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-β-D-arabinofuranosyl>uracil

• 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-<1-C-Acetonyl-2-bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-β-D-arabinofuranosyl>uracil
• 英文别名: 1-[(2R,3S,4R,5R)-3-bromo-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-(2-oxopropyl)oxolan-2-yl]pyrimidine-2,4-dione
• 化学式: C₂₄H₄₃BrN₂O₆Si₂
• 分子量: 591.69
• InChiKey: WNSWDXREEVCTMQ-ZHNFZGJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.74
• 重原子数：
  35
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  94.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1-(trimethylsilyl)propan-2-one 、 1-<2-Bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-1-(pivaloyloxy)-β-D-arabinofuranosyl>uracil 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以30%的产率得到1-<1-C-Acetonyl-2-bromo-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-β-D-arabinofuranosyl>uracil
  参考文献：
  名称：

  Anomeric manipulation of nucleosides: Stereosepecific entry to 1′-C-branched uracil nucleosides

  摘要：

  Uracil nucleosides variously branched at die anomeric position have been synthesized through stereoselective bromo-pivaloyloxylation of a 1',2'-unsaturated derivative and successive SnCl4-promoted nucleophilic substitution with organosilicon reagents. This constitutes the first example of C-C bond formation at the anomeric position of nucleoside.

  DOI：

  10.1016/s0040-4039(00)91829-x

文献信息

• 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.
• Anomeric manipulation of nucleosides: Stereosepecific entry to 1′-C-branched uracil nucleosides
  作者：Kazuhiro Haraguchi、Yoshiharu Itoh、Hiromichi Tanaka、Kentaro Yamaguchi、Tadashi Miyasaka

  DOI：10.1016/s0040-4039(00)91829-x

  日期：1993.10

  Uracil nucleosides variously branched at die anomeric position have been synthesized through stereoselective bromo-pivaloyloxylation of a 1',2'-unsaturated derivative and successive SnCl4-promoted nucleophilic substitution with organosilicon reagents. This constitutes the first example of C-C bond formation at the anomeric position of nucleoside.
• 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.