9-[2,3,5-tri-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl]-6-chloro-8-triisopropylsilylpurine | 249757-24-2

• 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-[2,3,5-tri-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl]-6-chloro-8-triisopropylsilylpurine
• 英文别名: [9-[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-6-chloropurin-8-yl]-tri(propan-2-yl)silane
• CAS: 249757-24-2
• 化学式: C₃₇H₇₃ClN₄O₄Si₄
• 分子量: 785.806
• InChiKey: IVSIQJBGQRMUEN-JHZZHVAFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.07
• 重原子数：
  50
• 可旋转键数：
  15
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  80.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  9-[2,3,5-tri-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl]-6-chloro-8-triisopropylsilylpurine 、 lithium diisopropyl amide 以 四氢呋喃 为溶剂， 以88%的产率得到2,3,5-tri-O-(tert-butyldimethylsilyl)-N,N-diisopropyl-8-triisopropylsilyladenosine
  参考文献：
  名称：

  First Evident Generation of Purin-2-yllithium:  Lithiation of an 8-Silyl-Protected 6-Chloropurine Riboside as a Key Step for the Synthesis of 2-Carbon-Substituted Adenosines

  摘要：

  Lithiation at the 2-position of purine ring has been accomplished for the first time by using 6-chloro-9-(2,3-O-isopropylidene-5-O-trityl-beta-D-ribofuranosyl)-8-(triisopropylsilyl)purine (7) as a substrate and LTMP as a lithiating agent. The 8-triisopropylsilyl group in 7 did not undergo anionic migration and, thus, allowed the ready generation of the C2-lithiated species by preventing deprotonation at the 8-position. The electron-withdrawing B-chlorine atom plays an essential role to this C2-lithiation. Reactions of the lithiated species with electrophiles gave the 8-substituted products (Me, Et, i-Pr, CH(OH)C6H11, C(OH)Me-2, CHO, CO2Me, and I) mostly in good yields. Ammonolysis of the 6-chlorine atom of these products (heating at 110 degrees C in a sealed tube with NH3/MeOH) effected simultaneous desilylation at the 8-position to give the corresponding adenosine analogues. The whole sequence provides a new and highly general method for the synthesis of 2-substituted adenosines.

  DOI：

  10.1021/jo9906577
• 作为产物：
  描述：

  三异丙基氯硅烷 、 6-chloro-9-(2,3,5-tris-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl)-9H-purine 在 六甲基磷酰三胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 以99%的产率得到9-[2,3,5-tri-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl]-6-chloro-8-triisopropylsilylpurine
  参考文献：
  名称：

  First Evident Generation of Purin-2-yllithium:  Lithiation of an 8-Silyl-Protected 6-Chloropurine Riboside as a Key Step for the Synthesis of 2-Carbon-Substituted Adenosines

  摘要：

  Lithiation at the 2-position of purine ring has been accomplished for the first time by using 6-chloro-9-(2,3-O-isopropylidene-5-O-trityl-beta-D-ribofuranosyl)-8-(triisopropylsilyl)purine (7) as a substrate and LTMP as a lithiating agent. The 8-triisopropylsilyl group in 7 did not undergo anionic migration and, thus, allowed the ready generation of the C2-lithiated species by preventing deprotonation at the 8-position. The electron-withdrawing B-chlorine atom plays an essential role to this C2-lithiation. Reactions of the lithiated species with electrophiles gave the 8-substituted products (Me, Et, i-Pr, CH(OH)C6H11, C(OH)Me-2, CHO, CO2Me, and I) mostly in good yields. Ammonolysis of the 6-chlorine atom of these products (heating at 110 degrees C in a sealed tube with NH3/MeOH) effected simultaneous desilylation at the 8-position to give the corresponding adenosine analogues. The whole sequence provides a new and highly general method for the synthesis of 2-substituted adenosines.

  DOI：

  10.1021/jo9906577

文献信息

• First Evident Generation of Purin-2-yllithium:  Lithiation of an 8-Silyl-Protected 6-Chloropurine Riboside as a Key Step for the Synthesis of 2-Carbon-Substituted Adenosines
  作者：Hiroki Kumamoto、Hiromichi Tanaka、Ryota Tsukioka、Yumiko Ishida、Akiko Nakamura、Satoe Kimura、Hiroyuki Hayakawa、Keisuke Kato、Tadashi Miyasaka

  DOI：10.1021/jo9906577

  日期：1999.10.1

  Lithiation at the 2-position of purine ring has been accomplished for the first time by using 6-chloro-9-(2,3-O-isopropylidene-5-O-trityl-beta-D-ribofuranosyl)-8-(triisopropylsilyl)purine (7) as a substrate and LTMP as a lithiating agent. The 8-triisopropylsilyl group in 7 did not undergo anionic migration and, thus, allowed the ready generation of the C2-lithiated species by preventing deprotonation at the 8-position. The electron-withdrawing B-chlorine atom plays an essential role to this C2-lithiation. Reactions of the lithiated species with electrophiles gave the 8-substituted products (Me, Et, i-Pr, CH(OH)C6H11, C(OH)Me-2, CHO, CO2Me, and I) mostly in good yields. Ammonolysis of the 6-chlorine atom of these products (heating at 110 degrees C in a sealed tube with NH3/MeOH) effected simultaneous desilylation at the 8-position to give the corresponding adenosine analogues. The whole sequence provides a new and highly general method for the synthesis of 2-substituted adenosines.