9-(2,5-Bis-O-(tert-butyldimethylsilyl)-3-deoxy-3-((methoxycarbonyl)methylidene)-β-D-ribofuranosyl)adenine | 152965-07-6

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷
• 英文名称: 9-(2,5-Bis-O-(tert-butyldimethylsilyl)-3-deoxy-3-((methoxycarbonyl)methylidene)-β-D-ribofuranosyl)adenine
• 英文别名: 9-{2,5-Bis-O-(tert-butyldimethylsilyl)-3-deoxy-3-[(methoxycarbonyl)methylidene]-β-D-ribofuranosyl}adenine；methyl (2Z)-2-[(2S,4R,5R)-5-(6-aminopurin-9-yl)-4-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-3-ylidene]acetate
• CAS: 152965-07-6
• 化学式: C₂₅H₄₃N₅O₅Si₂
• 分子量: 549.818
• InChiKey: IIEWEXSYSWGDQR-OULXLZJLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  37
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  124
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  9-(2,5-Bis-O-(tert-butyldimethylsilyl)-3-deoxy-3-((methoxycarbonyl)methylidene)-β-D-ribofuranosyl)adenine 在 palladium on activated charcoal 正丁基锂 、 氢气 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 74.67h， 生成 9-(2,5-Bis-O-(tert-butyldimethylsilyl)-3-deoxy-3-((((diethoxyphosphinyl)methyl)carbonyl)methylene)-β-D-ribofuranosyl)adenine
  参考文献：
  名称：

  Synthesis of nucleoside 3'-alkylphosphonates: intermediates for assembly of carbon-bridge dinucleotide analogs

  摘要：

  Several 3'-modified nucleosides have been prepared, through an initial Wittig or Horner-Wadsworth-Emmons condensation with an adenosine 3'-ketone, followed by catalytic hydrogenation of the resulting olefin. Subsequent reaction of the 3'alpha-methylene carboxylate with the lithium salt of diethyl ethylphosphonate gave a beta-keto phosphonate, while reaction of the methylene carboxylate with LDA, diethyl chlorophosphite, and O2 gives the corresponding alpha-phosphono ester. These new nucleoside phosphonates can be viewed as analogues of natural phosphates and also can serve as synthetic intermediates for preparation of carbon-bridged dinucleotide analogues. To give the first such example, the beta-keto phosphonate 13 was allowed to react with a nucleoside 5-aldehyde, affording the dinucleoside enone 23.

  DOI：

  10.1021/jo00079a027
• 作为产物：
  描述：

  9-(2,5-di-O-tert-butyldimethylsilyl-β-D-erythro-pentofuran-3-ulosyl)adenosine 、 甲氧羰基亚甲基三苯基正膦 以 四氢呋喃 为溶剂， 反应 7.0h， 以88%的产率得到9-(2,5-Bis-O-(tert-butyldimethylsilyl)-3-deoxy-3-((methoxycarbonyl)methylidene)-β-D-ribofuranosyl)adenine
  参考文献：
  名称：

  Synthesis of nucleoside 3'-alkylphosphonates: intermediates for assembly of carbon-bridge dinucleotide analogs

  摘要：

  Several 3'-modified nucleosides have been prepared, through an initial Wittig or Horner-Wadsworth-Emmons condensation with an adenosine 3'-ketone, followed by catalytic hydrogenation of the resulting olefin. Subsequent reaction of the 3'alpha-methylene carboxylate with the lithium salt of diethyl ethylphosphonate gave a beta-keto phosphonate, while reaction of the methylene carboxylate with LDA, diethyl chlorophosphite, and O2 gives the corresponding alpha-phosphono ester. These new nucleoside phosphonates can be viewed as analogues of natural phosphates and also can serve as synthetic intermediates for preparation of carbon-bridged dinucleotide analogues. To give the first such example, the beta-keto phosphonate 13 was allowed to react with a nucleoside 5-aldehyde, affording the dinucleoside enone 23.

  DOI：

  10.1021/jo00079a027

文献信息

• Synthesis of nucleoside 3'-alkylphosphonates: intermediates for assembly of carbon-bridge dinucleotide analogs
  作者：Koo Lee、David F. Wiemer

  DOI：10.1021/jo00079a027

  日期：1993.12

  Several 3'-modified nucleosides have been prepared, through an initial Wittig or Horner-Wadsworth-Emmons condensation with an adenosine 3'-ketone, followed by catalytic hydrogenation of the resulting olefin. Subsequent reaction of the 3'alpha-methylene carboxylate with the lithium salt of diethyl ethylphosphonate gave a beta-keto phosphonate, while reaction of the methylene carboxylate with LDA, diethyl chlorophosphite, and O2 gives the corresponding alpha-phosphono ester. These new nucleoside phosphonates can be viewed as analogues of natural phosphates and also can serve as synthetic intermediates for preparation of carbon-bridged dinucleotide analogues. To give the first such example, the beta-keto phosphonate 13 was allowed to react with a nucleoside 5-aldehyde, affording the dinucleoside enone 23.