6-chloro-9-(2,3-O-isopropylidene-5-O-trityl-β-D-ribofuranosyl)purine | 249757-27-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 6-chloro-9-(2,3-O-isopropylidene-5-O-trityl-β-D-ribofuranosyl)purine
• 英文别名: 9-[(3aR,4R,6R,6aR)-2,2-dimethyl-6-(trityloxymethyl)-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-6-chloropurine
• CAS: 249757-27-5
• 化学式: C₃₂H₂₉ClN₄O₄
• 分子量: 569.06
• InChiKey: CDAHJRRFOMTDDH-BQOYKFDPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  41
• 可旋转键数：
  7
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.28
• 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：

  6-chloro-9-(2,3-O-isopropylidene-5-O-trityl-β-D-ribofuranosyl)purine 在 六甲基磷酰三胺 、 2,2,6,6-tetramethylpiperidinyl-lithium 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 0.16h， 生成 6-chloro-2-(1-hydroxy-1-methyl)ethyl-9-(2,3-O-isopropylidene-5-O-trityl-β-D-ribofuranosyl)-8-(triisopropylsilyl)purine
  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：

  三苯基氯甲烷 、 6-氯-9-beta-D-(2,3-异亚丙基)呋喃核糖基嘌呤 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 以95%的产率得到6-chloro-9-(2,3-O-isopropylidene-5-O-trityl-β-D-ribofuranosyl)purine
  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.