1β-(6-aminopyridin-3-yl)-1,2-dideoxy-3,5-di-O-(t-butyldimethylsilyl)-D-ribofuranose | 950830-66-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1β-(6-aminopyridin-3-yl)-1,2-dideoxy-3,5-di-O-(t-butyldimethylsilyl)-D-ribofuranose
• 英文别名: 2-amino-5-[3’,5’-di-O-tert-butyldimethylsilyl-(2’-deoxy-D-ribofuranosyl)]pyridine；5-[(2R,4S,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]pyridin-2-amine
• CAS: 950830-66-7
• 化学式: C₂₂H₄₂N₂O₃Si₂
• 分子量: 438.758
• InChiKey: QFIWMFICPDSIOW-CEXWTWQISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.91
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  66.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1β-(6-aminopyridin-3-yl)-1,2-dideoxy-3,5-di-O-(t-butyldimethylsilyl)-D-ribofuranose 在 triethylamine tris(hydrogen fluoride) 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以90%的产率得到2-Amino-5-(2'-deoxy-β-D-ribofuranosyl)pyridine
  参考文献：
  名称：

  Modular and Practical Synthesis of 6-Substituted Pyridin-3-yl C-Nucleosides

  摘要：

  A novel modular and practical methodology for preparation of 6-substituted pyridin-3-yl C-nucleosides was developed. The Heck reaction of 2-chloro-5-iodopyridine with a 3'-TBDMS-protected glycal gave a 6-chloropyridin-3-yl nucleoside analogue, which was then desilylated, selectively reduced, and reprotected to give the TBDMS-protected 6-chloropyridin-3-yl C-2'-deoxyribonucleoside as a pure beta-anomer in a total yield of 39% over four steps. This key intermediate was then subjected to a series of palladium-catalyzed cross-coupling reactions, aminations, and alkoxylations to give a series of protected 1 beta-(6-alkyl-, 6-aryl-, 6-hetaryl, 6-amino-, and 6-tert-butoxypyridin-3-yl)-2'-deoxyribonucleosides. 6-Unsubstituted pyridin-3-yl C-nucleoside was prepared by catalytic hydrogenation of the chloro derivative and 6-oxopyridine C-nucleoside by treatment of the 6-tert-butoxy derivative with TFA. Deprotection of all the silylated nucleosides by Et3N center dot 3HF gave a series of free C-nucleosides (10 examples).

  DOI：

  10.1021/jo0709504
• 作为产物：
  描述：

  1β-(6-chloropyridin-3-yl)-1,2-dideoxy-3,5-di-O-(tert-butyldimethylsilyl)-D-ribofuranose 在 tris(dibenzylideneacetone)dipalladium (0) lithium hexamethyldisilazane 、 2-(二环己基膦基)联苯 作用下， 以 四氢呋喃 为溶剂， 反应 21.0h， 以90%的产率得到1β-(6-aminopyridin-3-yl)-1,2-dideoxy-3,5-di-O-(t-butyldimethylsilyl)-D-ribofuranose
  参考文献：
  名称：

  Modular and Practical Synthesis of 6-Substituted Pyridin-3-yl C-Nucleosides

  摘要：

  A novel modular and practical methodology for preparation of 6-substituted pyridin-3-yl C-nucleosides was developed. The Heck reaction of 2-chloro-5-iodopyridine with a 3'-TBDMS-protected glycal gave a 6-chloropyridin-3-yl nucleoside analogue, which was then desilylated, selectively reduced, and reprotected to give the TBDMS-protected 6-chloropyridin-3-yl C-2'-deoxyribonucleoside as a pure beta-anomer in a total yield of 39% over four steps. This key intermediate was then subjected to a series of palladium-catalyzed cross-coupling reactions, aminations, and alkoxylations to give a series of protected 1 beta-(6-alkyl-, 6-aryl-, 6-hetaryl, 6-amino-, and 6-tert-butoxypyridin-3-yl)-2'-deoxyribonucleosides. 6-Unsubstituted pyridin-3-yl C-nucleoside was prepared by catalytic hydrogenation of the chloro derivative and 6-oxopyridine C-nucleoside by treatment of the 6-tert-butoxy derivative with TFA. Deprotection of all the silylated nucleosides by Et3N center dot 3HF gave a series of free C-nucleosides (10 examples).

  DOI：

  10.1021/jo0709504

文献信息

• A 2-AMINO-6-METHYLPYRIDIN-5-YL NUCLEOBASE FOR GC BASE PAIR RECOGNITION IN THE PARALLEL TRIPLEX DNA
  作者：Yoshiyuki Hari、Motoi Nakahara、Satoshi Obika

  DOI：10.3987/com-12-s(n)68

  日期：——

  DNA triple helices containing consecutive C+H center dot GC triplets are unstable at neutral pH because protonations of cytosines into the third strand are necessary. Previously, a 2-aminopyridin-5-yl nucleobase (P) was developed and has been widely used as a substitute for the cytosine nucleobase. In this work, we designed a 2-amino-6-methylpyridin-5-yl nucleobase (P-Me), which could preferentially adopt an anti-orientation by the 6-methyl group. This might lead to formation of a stable base triplet with a GC base pair compared to P. We also synthesized 15-mer triplex-forming oligonucleotides (TFOs) containing P-Me by the standard solid-phase method and evaluated the triplex stability of the TFOs at neutral pH by UV melting experiments.
• Modular and Practical Synthesis of 6-Substituted Pyridin-3-yl C-Nucleosides
  作者：Nicolas Joubert、Radek Pohl、Blanka Klepetářová、Michal Hocek

  DOI：10.1021/jo0709504

  日期：2007.8.31

  A novel modular and practical methodology for preparation of 6-substituted pyridin-3-yl C-nucleosides was developed. The Heck reaction of 2-chloro-5-iodopyridine with a 3'-TBDMS-protected glycal gave a 6-chloropyridin-3-yl nucleoside analogue, which was then desilylated, selectively reduced, and reprotected to give the TBDMS-protected 6-chloropyridin-3-yl C-2'-deoxyribonucleoside as a pure beta-anomer in a total yield of 39% over four steps. This key intermediate was then subjected to a series of palladium-catalyzed cross-coupling reactions, aminations, and alkoxylations to give a series of protected 1 beta-(6-alkyl-, 6-aryl-, 6-hetaryl, 6-amino-, and 6-tert-butoxypyridin-3-yl)-2'-deoxyribonucleosides. 6-Unsubstituted pyridin-3-yl C-nucleoside was prepared by catalytic hydrogenation of the chloro derivative and 6-oxopyridine C-nucleoside by treatment of the 6-tert-butoxy derivative with TFA. Deprotection of all the silylated nucleosides by Et3N center dot 3HF gave a series of free C-nucleosides (10 examples).