[(4aR,6S,7R,7aS)-2,2-ditert-butyl-6-(2,4-dimethoxypyrimidin-5-yl)-4a,6,7,7a-tetrahydro-4H-thieno[3,2-d][1,3,2]dioxasilin-7-yl] acetate | 1335287-36-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(4aR,6S,7R,7aS)-2,2-ditert-butyl-6-(2,4-dimethoxypyrimidin-5-yl)-4a,6,7,7a-tetrahydro-4H-thieno[3,2-d][1,3,2]dioxasilin-7-yl] acetate
• CAS: 1335287-36-9
• 化学式: C₂₁H₃₄N₂O₆SSi
• 分子量: 470.662
• InChiKey: VJQQFEFYHDHLLY-VQHPVUNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.04
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  [(4aR,6S,7R,7aS)-2,2-ditert-butyl-6-(2,4-dimethoxypyrimidin-5-yl)-4a,6,7,7a-tetrahydro-4H-thieno[3,2-d][1,3,2]dioxasilin-7-yl] acetate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 7.5h， 生成 5-[2,3,5-tri-O-acetyl-4-thio-β-D-ribofuranosyl]-2,4-dimethoxypyrimidine
  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：

  2,4-二甲氧基-5-碘嘧啶 在 4-二甲氨基吡啶 、 copper(l) iodide 、 四(三苯基膦)钯 、 硼烷四氢呋喃络合物 、 双氧水 、 N,N-二异丙基乙胺 、 sodium hydroxide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 21.0h， 生成 [(4aR,6S,7R,7aS)-2,2-ditert-butyl-6-(2,4-dimethoxypyrimidin-5-yl)-4a,6,7,7a-tetrahydro-4H-thieno[3,2-d][1,3,2]dioxasilin-7-yl] acetate 、 [2-[(4S,5R)-5-[[(4S,5R)-4-[2-acetyloxy-2-(2,4-dimethoxypyrimidin-5-yl)ethyl]-2,2-ditert-butyl-1,3,2-dioxasilinan-5-yl]disulfanyl]-2,2-ditert-butyl-1,3,2-dioxasilinan-4-yl]-1-(2,4-dimethoxypyrimidin-5-yl)ethyl] acetate
  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