5'-azido-2'-O-(tert-butyldimethylsilyl)-3'-[[N-(2',3'-bis-O-(tert-butyldimethylsilyl)-5'-deoxyuridin-5'-yl)carbamoyl]methyl]-3',5'-dideoxyuridine | 251296-93-2

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 5'-脱氧核糖核苷
• 英文名称: 5'-azido-2'-O-(tert-butyldimethylsilyl)-3'-[[N-(2',3'-bis-O-(tert-butyldimethylsilyl)-5'-deoxyuridin-5'-yl)carbamoyl]methyl]-3',5'-dideoxyuridine
• 英文别名: 2-[(2S,3R,4R,5R)-2-(azidomethyl)-4-[tert-butyl(dimethyl)silyl]oxy-5-(2,4-dioxopyrimidin-1-yl)oxolan-3-yl]-N-[[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-(2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl]acetamide
• CAS: 251296-93-2
• 化学式: C₃₈H₆₆N₈O₁₀Si₃
• 分子量: 879.246
• InChiKey: QKDAWGZTQLTTFB-SHOCMBFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.49
• 重原子数：
  59
• 可旋转键数：
  17
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  188
• 氢给体数：
  3
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  5'-azido-2'-O-(tert-butyldimethylsilyl)-3'-[[N-(2',3'-bis-O-(tert-butyldimethylsilyl)-5'-deoxyuridin-5'-yl)carbamoyl]methyl]-3',5'-dideoxyuridine 在 palladium on activated charcoal 氢气 作用下， 以 四氢呋喃 为溶剂， 20.0 ℃ 、34.47 kPa 条件下， 反应 8.0h， 以63%的产率得到5'-amino-2'-O-(tert-butyldimethylsilyl)-3'-[[N-(2',3'-bis-O-(tert-butyldimethylsilyl)-5'-deoxyuridin-5'-yl)carbamoyl]methyl]-3',5'-dideoxyuridine
  参考文献：
  名称：

  Amide-Linked Ribonucleoside Dimers Derived from 5‘-Amino-5‘-deoxy- and 3‘-(Carboxymethyl)-3‘-deoxynucleoside Precursors¹

  摘要：

  Treatment of tert-butyldimethylsilyl (TBDMS) derivatives of 3'-keto(adenosine or uridine) with [(ethoxycarbonyl)methylene]triphenylphosphorane gave exocyclic alkenes that underwent stereoselective hydrogenation to give 3'-deoxy-3'-[(ethoxycarbonyl)methyl](Ado or Urd) analogues. Saponification provided the 3'-(carboxymethyl)-3'-deoxy(Ado and Urd) derivatives 37 and 38. Treatment of 37 or 38 with DCC and 5'-amino-2',3'-bis-O-TBDMS-5'-deoxynucleosides gave the amide-linked dimers (74-82%). Activation of 37 or 38 with 4-nitrophenol/DCC, and direct coupling of the 4-nitrophenyl esters with 5'-amino-5'-deoxy(Ado or Urd) in pyridine also produced amide dimers efficiently (65-70%). Analogous activation of a 5'-O-DMT-protected carboxylate, and its coupling with 5'-amino-5'-deoxy-2'-O-methyladenosine gave the amide dimer in good yield (74%). Coupling (DCC) of a 5'-azido-2'-O-TBDMS-3'-(carboxymethyl)-3', 5'-dideoxyuridine intermediate with 5'-amino-5'-deoxynucleosides gave amide-linked dimers (72-78%) that can serve as masked (azide reduction) 5'-amino dimers for analogous synthesis of extended amide-linked oligomers.

  DOI：

  10.1021/jo9908647
• 作为产物：
  描述：

  5'-azido-5'-deoxyuridine 在 咪唑 、 1,3-丙二硫醇 、 三乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 吡啶 、 乙醇 、 二氯甲烷 为溶剂， 反应 42.0h， 生成 5'-azido-2'-O-(tert-butyldimethylsilyl)-3'-[[N-(2',3'-bis-O-(tert-butyldimethylsilyl)-5'-deoxyuridin-5'-yl)carbamoyl]methyl]-3',5'-dideoxyuridine
  参考文献：
  名称：

  Amide-Linked Ribonucleoside Dimers Derived from 5‘-Amino-5‘-deoxy- and 3‘-(Carboxymethyl)-3‘-deoxynucleoside Precursors¹

  摘要：

  Treatment of tert-butyldimethylsilyl (TBDMS) derivatives of 3'-keto(adenosine or uridine) with [(ethoxycarbonyl)methylene]triphenylphosphorane gave exocyclic alkenes that underwent stereoselective hydrogenation to give 3'-deoxy-3'-[(ethoxycarbonyl)methyl](Ado or Urd) analogues. Saponification provided the 3'-(carboxymethyl)-3'-deoxy(Ado and Urd) derivatives 37 and 38. Treatment of 37 or 38 with DCC and 5'-amino-2',3'-bis-O-TBDMS-5'-deoxynucleosides gave the amide-linked dimers (74-82%). Activation of 37 or 38 with 4-nitrophenol/DCC, and direct coupling of the 4-nitrophenyl esters with 5'-amino-5'-deoxy(Ado or Urd) in pyridine also produced amide dimers efficiently (65-70%). Analogous activation of a 5'-O-DMT-protected carboxylate, and its coupling with 5'-amino-5'-deoxy-2'-O-methyladenosine gave the amide dimer in good yield (74%). Coupling (DCC) of a 5'-azido-2'-O-TBDMS-3'-(carboxymethyl)-3', 5'-dideoxyuridine intermediate with 5'-amino-5'-deoxynucleosides gave amide-linked dimers (72-78%) that can serve as masked (azide reduction) 5'-amino dimers for analogous synthesis of extended amide-linked oligomers.

  DOI：

  10.1021/jo9908647

文献信息

• Amide-Linked Ribonucleoside Dimers Derived from 5‘-Amino-5‘-deoxy- and 3‘-(Carboxymethyl)-3‘-deoxynucleoside Precursors¹
  作者：Matt A. Peterson、Bradley L. Nilsson、Sanchita Sarker、Bogdan Doboszewski、Weijian Zhang、Morris J. Robins

  DOI：10.1021/jo9908647

  日期：1999.10.1

  Treatment of tert-butyldimethylsilyl (TBDMS) derivatives of 3'-keto(adenosine or uridine) with [(ethoxycarbonyl)methylene]triphenylphosphorane gave exocyclic alkenes that underwent stereoselective hydrogenation to give 3'-deoxy-3'-[(ethoxycarbonyl)methyl](Ado or Urd) analogues. Saponification provided the 3'-(carboxymethyl)-3'-deoxy(Ado and Urd) derivatives 37 and 38. Treatment of 37 or 38 with DCC and 5'-amino-2',3'-bis-O-TBDMS-5'-deoxynucleosides gave the amide-linked dimers (74-82%). Activation of 37 or 38 with 4-nitrophenol/DCC, and direct coupling of the 4-nitrophenyl esters with 5'-amino-5'-deoxy(Ado or Urd) in pyridine also produced amide dimers efficiently (65-70%). Analogous activation of a 5'-O-DMT-protected carboxylate, and its coupling with 5'-amino-5'-deoxy-2'-O-methyladenosine gave the amide dimer in good yield (74%). Coupling (DCC) of a 5'-azido-2'-O-TBDMS-3'-(carboxymethyl)-3', 5'-dideoxyuridine intermediate with 5'-amino-5'-deoxynucleosides gave amide-linked dimers (72-78%) that can serve as masked (azide reduction) 5'-amino dimers for analogous synthesis of extended amide-linked oligomers.