4-bromo-2-[2-(triethylsilyl)-3,5-O-(di-tert-butylsilylene)-4-thio-D-erythro-pentofuranosyl]thiazole | 1335287-44-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4-bromo-2-[2-(triethylsilyl)-3,5-O-(di-tert-butylsilylene)-4-thio-D-erythro-pentofuranosyl]thiazole
• 英文别名: [(4aR,6R,7R,7aS)-6-(4-bromo-1,3-thiazol-2-yl)-2,2-ditert-butyl-4a,6,7,7a-tetrahydro-4H-thieno[3,2-d][1,3,2]dioxasilin-7-yl]oxy-triethylsilane
• CAS: 1335287-44-9
• 化学式: C₂₂H₄₀BrNO₃S₂Si₂
• 分子量: 566.771
• InChiKey: WZBFCDXOLAGPFV-NXWXRZEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.91
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  94.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-bromo-2-[2-(triethylsilyl)-3,5-O-(di-tert-butylsilylene)-4-thio-D-erythro-pentofuranosyl]thiazole 、 氯甲酸乙酯 在 叔丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.25h， 以22%的产率得到2-[2-(triethylsilyl)-3,5-O-(di-tert-butylsilylene)-4-thio-D-erythro-pentofuranosyl]-4-ethoxycarbonylthiazole
  参考文献：
  名称：

  An Access to the β-Anomer of 4′-Thio-C-ribonucleosides: Hydroboration of 1-C-Aryl- or 1-C-Heteroaryl-4-thiofuranoid Glycals and Its Regiochemical Outcome

  摘要：

  We have developed a novel method for the synthesis of the beta-anomer of 4'-thio-C-ribonucleosides from 3,5-O-(di-tert-butylsilylene)-4-thiofuranoid glycal. Palladium-catalyzed coupling of 1-tributylstannyl-4-thiofuranoid glycal with iodobenzene or a heteroaryl halide gave 1-C-phenyl- or 1-C-heteroaryl-glycals. Hydroboration of these glycals proceeded at the alpha-face, and subsequent alkaline hydrogen peroxide treatment of the resulting 2'-alpha-borane furnished the respective beta-anomer of 4'-thio-C-ribonucleosides. These results demonstrate that this synthetic method has a wider scope in terms of heterocyclic base structure. During this study, unexpected Markovnikov-oriented hydroboration has been observed to lead to the respective 1'-alpha-boranes. These 1'-boranes were converted into either the ring-opened structure or the 2'-deoxy derivatives depending upon their stability.

  DOI：

  10.1021/jo201100n
• 作为产物：
  描述：

  在 咪唑 、 双氧水 、 sodium hydroxide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 4-bromo-2-[2-(triethylsilyl)-3,5-O-(di-tert-butylsilylene)-4-thio-D-erythro-pentofuranosyl]thiazole
  参考文献：
  名称：

  An Access to the β-Anomer of 4′-Thio-C-ribonucleosides: Hydroboration of 1-C-Aryl- or 1-C-Heteroaryl-4-thiofuranoid Glycals and Its Regiochemical Outcome

  摘要：

  We have developed a novel method for the synthesis of the beta-anomer of 4'-thio-C-ribonucleosides from 3,5-O-(di-tert-butylsilylene)-4-thiofuranoid glycal. Palladium-catalyzed coupling of 1-tributylstannyl-4-thiofuranoid glycal with iodobenzene or a heteroaryl halide gave 1-C-phenyl- or 1-C-heteroaryl-glycals. Hydroboration of these glycals proceeded at the alpha-face, and subsequent alkaline hydrogen peroxide treatment of the resulting 2'-alpha-borane furnished the respective beta-anomer of 4'-thio-C-ribonucleosides. These results demonstrate that this synthetic method has a wider scope in terms of heterocyclic base structure. During this study, unexpected Markovnikov-oriented hydroboration has been observed to lead to the respective 1'-alpha-boranes. These 1'-boranes were converted into either the ring-opened structure or the 2'-deoxy derivatives depending upon their stability.

  DOI：

  10.1021/jo201100n

文献信息

• An Access to the β-Anomer of 4′-Thio-C-ribonucleosides: Hydroboration of 1-<i>C</i>-Aryl- or 1-<i>C</i>-Heteroaryl-4-thiofuranoid Glycals and Its Regiochemical Outcome
  作者：Kazuhiro Haraguchi、Chikafumi Horii、Yuichi Yoshimura、Fumiko Ariga、Aya Tadokoro、Hiromichi Tanaka

  DOI：10.1021/jo201100n

  日期：2011.11.4

  We have developed a novel method for the synthesis of the beta-anomer of 4'-thio-C-ribonucleosides from 3,5-O-(di-tert-butylsilylene)-4-thiofuranoid glycal. Palladium-catalyzed coupling of 1-tributylstannyl-4-thiofuranoid glycal with iodobenzene or a heteroaryl halide gave 1-C-phenyl- or 1-C-heteroaryl-glycals. Hydroboration of these glycals proceeded at the alpha-face, and subsequent alkaline hydrogen peroxide treatment of the resulting 2'-alpha-borane furnished the respective beta-anomer of 4'-thio-C-ribonucleosides. These results demonstrate that this synthetic method has a wider scope in terms of heterocyclic base structure. During this study, unexpected Markovnikov-oriented hydroboration has been observed to lead to the respective 1'-alpha-boranes. These 1'-boranes were converted into either the ring-opened structure or the 2'-deoxy derivatives depending upon their stability.