N²-acetyl-9-(2,3,5-tri-O-acetyl-α-D-arabinofuranosyl)-O⁶-diphenylcarbamoylguanine | 112233-76-8

• 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: N²-acetyl-9-(2,3,5-tri-O-acetyl-α-D-arabinofuranosyl)-O⁶-diphenylcarbamoylguanine
• 英文别名: 2-N-acetyl-9-(2,3,5-tri-O-acetyl-α-D-arabinofuranosyl)-6-O-(diphenylcarbamoyl)guanine；[(2R,3R,4S,5S)-5-[2-acetamido-6-(diphenylcarbamoyloxy)purin-9-yl]-3,4-diacetyloxyoxolan-2-yl]methyl acetate
• CAS: 112233-76-8
• 化学式: C₃₁H₃₀N₆O₁₀
• 分子量: 646.613
• InChiKey: XSSWDMURTPAIDU-OUYCBEJASA-N

物化性质

• 密度：
  1.45±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  47
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  190
• 氢给体数：
  1
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  N²-acetyl-9-(2,3,5-tri-O-acetyl-α-D-arabinofuranosyl)-O⁶-diphenylcarbamoylguanine 在 ammonium hydroxide 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以84%的产率得到9-(α-D-arabinofuranosyl)guanine
  参考文献：
  名称：

  Nucleic Acid Related Compounds. 93. A Solution for the Historic Problem of Regioselective Sugar−Base Coupling To Produce 9-Glycosylguanines or 7-Glycosylguanines¹

  摘要：

  Per(trimethylsilyl)-2-N-acylguanine derivatives and tetra-O-acylpentofuranoses were coupled [tin-(IV) chloride or titanium(IV) chloride catalysis] to give predominant formation of 7-glycosylguanines. With TiCl4, a fortuitous organic/aqueous partitioning allowed isolation of 7-glycosylguanines from the 7/9 isomer mixtures. Per(trimethylsilyl)-2-N-acyl-6-O-(diphenylcarbamoyl)guanine derivatives and tetra-O-acylpentofuranoses underwent regioselective coupling (trimethylsilyl trifluoromethane-sulfonate catalysis) to give 9-glycosylguanines. The 6-O-(diphenylcarbamoyl)peracyl-9-beta-D-ribofuranosyl isomer was shown to be both the kinetic and thermodynamic coupling product. Deprotection of all of the peracyl coupling products was effected under mild conditions to give good to high yields of guanine nucleoside analogues. These methodologies provide solutions for the regioselective synthesis of 7- and 9-glycosylguanine nucleosides.

  DOI：

  10.1021/jo9617023
• 作为产物：
  描述：

  二苯氨基甲酰氯 在 苯磺酰胺 、 三氟甲磺酸三甲基硅酯 、 N,N-二异丙基乙胺 作用下， 以 吡啶 为溶剂， 反应 2.25h， 生成 N²-acetyl-9-(2,3,5-tri-O-acetyl-α-D-arabinofuranosyl)-O⁶-diphenylcarbamoylguanine
  参考文献：
  名称：

  Nucleic Acid Related Compounds. 93. A Solution for the Historic Problem of Regioselective Sugar−Base Coupling To Produce 9-Glycosylguanines or 7-Glycosylguanines¹

  摘要：

  Per(trimethylsilyl)-2-N-acylguanine derivatives and tetra-O-acylpentofuranoses were coupled [tin-(IV) chloride or titanium(IV) chloride catalysis] to give predominant formation of 7-glycosylguanines. With TiCl4, a fortuitous organic/aqueous partitioning allowed isolation of 7-glycosylguanines from the 7/9 isomer mixtures. Per(trimethylsilyl)-2-N-acyl-6-O-(diphenylcarbamoyl)guanine derivatives and tetra-O-acylpentofuranoses underwent regioselective coupling (trimethylsilyl trifluoromethane-sulfonate catalysis) to give 9-glycosylguanines. The 6-O-(diphenylcarbamoyl)peracyl-9-beta-D-ribofuranosyl isomer was shown to be both the kinetic and thermodynamic coupling product. Deprotection of all of the peracyl coupling products was effected under mild conditions to give good to high yields of guanine nucleoside analogues. These methodologies provide solutions for the regioselective synthesis of 7- and 9-glycosylguanine nucleosides.

  DOI：

  10.1021/jo9617023

文献信息

• High-yield regioselective synthesis of 9-glycosyl guanine nucleosides and analogues via coupling with 2-<i>N</i>-acetyl-6-<i>O</i>-diphenylcarbamoylguanine
  作者：Ruiming Zou、Morris J. Robins

  DOI：10.1139/v87-243

  日期：1987.6.1

  Treatment of 2-N,9-diacetylguanine with diphenylcarbamoyl chloride followed by heating with aqueous ethanol gave 2-N-acetyl-6-O-diphenylcarbamoylguanine (2-acetamido-6-diphenylcarbamoyloxypurine). Bis-trimethylsilylation of this product followed by coupling with glycosyl acetates (trimethylsilyl triflate catalysis) or α-haloethers in anhydroustoluene gave 9-substituted guanine compounds in high yields

  用二苯基氨基甲酰氯处理 2-N,9-二乙酰鸟嘌呤，然后用乙醇水溶液加热，得到 2-N-乙酰基-6-O-二苯基氨基甲酰鸟嘌呤（2-乙酰氨基-6-二苯基氨基甲酰氧基嘌呤）。该产物的双三甲基甲硅烷基化，然后与乙酸糖酯（三氟甲磺酸三甲基甲硅烷酯催化）或无水甲苯中的 α-卤醚偶联，以高产率得到 9-取代的鸟嘌呤化合物，未检测到 7-异构体。
• Nucleotides. LXXIV Synthesis of a-D-Arabino-oligonucleotides
  作者：Christoph Henke、Wolfgang Pfleiderer

  DOI：10.1080/15257770500267113

  日期：2005.9.1

  The 5 alpha-D-arabinofuranosylnucleosides alpha-araU (15), alpha-araT (18), alpha-araC (22), alpha-araA (25), and alpha-araG (28) have been synthesized by the modified silyl-method. The amino groups at the nucleobases and the 2'-hydroxy group at the sugar moiety were protected by the 2-(4-nitro-phenyl) ethoxycarbonyl (npeoc) group (37-40) and the amide function in alpha-araG was additionally blocked by the 2-(4-nitrophenyl)ethyl group (63) to improve solubility in organic solvents. Mono-and dimethoxytritylation of the 5'-OH group was performed in the usual manner to give 41-48, 64, and 65 in high yields and further substitution of the 3'-OH group led to the monomeric building blocks 66-75 as well as the 3'-O-succinoyl derivatives 76-85 functioning as starting units in solid-support oligonucleotide synthesis. A large number of oligo-alpha-arabinonucleotides have been prepared on modified CPG-material applying the npeoc/npe strategy as a very efficient synthetic tool for highly purified, homogenous oligomers. Hybridizations between alpha-arabinonucleotide strands revealed in analogy to earlier findings an antiparallel orientation whereas the combination of an oligo-alpha-D-arabinonucleotide with a complementary oligo-2'-deoxy-beta-D-ribofuranosylnucleotide showed base-pairing only if a parallel polarity was present. The advantages in oligo-alpha-arabinonucleotide synthesis were furthermore demonstrated by the synthesis of the t alpha-ANA(his) a structural analog of the natural tRNA(his) of the phage T5.