6-chloro-2-iodo-9-{2,3,5-tri-O-[tert-butyl(dimethyl)silanyl]-β-D-ribofuranosyl}-9H-purine | 171613-04-0

• 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: 6-chloro-2-iodo-9-{2,3,5-tri-O-[tert-butyl(dimethyl)silanyl]-β-D-ribofuranosyl}-9H-purine
• 英文别名: 6-chloro-2-iodo-9-{2,3,5-tris-O-[tert-butyl(dimethyl)silyl]-β-D-ribofuranosyl}-9H-purine；[(2R,3R,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-(6-chloro-2-iodopurin-9-yl)oxolan-2-yl]methoxy-tert-butyl-dimethylsilane
• CAS: 171613-04-0
• 化学式: C₂₈H₅₂ClIN₄O₄Si₃
• 分子量: 755.359
• InChiKey: FYFMOELNCITMRZ-UMCMBGNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.78
• 重原子数：
  41
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 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-2-iodo-9-{2,3,5-tri-O-[tert-butyl(dimethyl)silanyl]-β-D-ribofuranosyl}-9H-purine 在 氟化铵 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 叔丁醇 为溶剂， 生成 N⁶-(2S-endo-norborn-5-en-2-yl)-2-iodoadenosine
  参考文献：
  名称：

  新的2，N6-二取代的腺苷：有效和选择性的A1腺苷受体激动剂。

  摘要：

  合成了许多在2和N6-位取代的腺苷类似物，并评估了对A1和A2A腺苷受体（AR）的亲和力，功能效能和内在活性。测试了三类N6-取代基；降冰片-2-基（系列1），降冰片-2-基（系列2）和5,6-环氧降冰片-2-基（系列3）。卤素；氟，溴和碘被评估为C-2取代基。所有化合物对仓鼠平滑肌DDT1 MF-2细胞的A1AR亲和力（纳米摩尔）相对较高，并且抑制（-）异丙肾上腺素刺激的cAMP蓄积的能力较高，每个系列中的2-氟衍生物均具有最高亲和力。所有衍生物均显示出与CPA相同的固有活性。在A2AAR，所有这些衍生物对于刺激大鼠嗜铬细胞瘤PC-12细胞中的cAMP积累均显示出较低的亲和力和效价（微摩尔）。与CGS 21680相比，衍生物的固有活性取决于C-2位的卤素取代基，其中大部分表现出部分激动剂活性。特别令人感兴趣的是2-碘-N6-（2S-内-降冰片-2-基）腺苷（5e），对A1AR的选择性超过

  DOI：

  10.1016/s0968-0896(01)00384-4
• 作为产物：
  描述：

  6-chloro-9-(2,3,5-tris-O-(tert-butyldimethylsilyl)-β-D-ribofuranosyl)-9H-purine 在 三丁基氯化锡 、 2,2,6,6-tetramethylpiperidinyl-lithium 、 碘 作用下， 生成 6-chloro-2-iodo-9-{2,3,5-tri-O-[tert-butyl(dimethyl)silanyl]-β-D-ribofuranosyl}-9H-purine
  参考文献：
  名称：

  A New Entry to 2-Substituted Purine Nucleosides Based on Lithiation-Mediated Stannyl Transfer of 6-Chloropurine Nucleosides

  摘要：

  In spite of exclusive lithiation at the 8-position of 9-(2,3,5-tris-O-TBDMS-beta-D-ribofuranosyl)-6-chloropurine (2) with LDA, subsequent quenching of its lithiated species with Bu3SnCl (or TMSCl) results in the formation of 2-substituted products. Under optimized reaction conditions, where LTMP was us ed as a lithiating agent, 9-(2,3,5-tris-O-TBDMS-beta-D-ribofuranosyl)-6-chloro-2-(tributylstannyl)purine (11) was formed in quantitative yield. Several experiments carried out to verify the reaction mechanism suggested that an anionic stannyl (or silyl) transfer from the 8- to the 2-position had been involved. Manipulation of the 2-tributylstannyl group in 11 and in its adenine counterpart (22) has disclosed a new entry to 2-substituted purine nucleosides. This chemistry was briefly applied to the synthesis of the 2-fluoro analogue of neplanocin A.

  DOI：

  10.1021/jo970398q

文献信息

• Lithiation-mediated CC silyl and stannyl migrations observed in 6-chloro-9-(β-d-ribofuranosyl)purine
  作者：Keisuke Kato、Hiroyuki Hayakawa、Hiromichi Tanaka、Hiroki Kumamoto、Tadashi Miyasaka

  DOI：10.1016/0040-4039(95)01302-x

  日期：1995.9

  Lithiation of 9-[2,3,5-tris-O-(tert-butyldimethylsilyl)-beta-D-ribofuranosyl]-6-chloropurine (1) with LTMP (lithium 2,2,6,6-tetramethylpiperidide) and a subsequent reaction with either Me(3)SiCl or Bu(3)SnCl was found to effect C-2-substitution, as a result of ''silyl or stannyl migration'' from C-8 to C-2 position. Transformation of the resulting 2-stannyl derivative (8) to 2-substituted adenosines was also examined briefly.