1β-(6-chloropyridin-3-yl)-1,2-dideoxy-3,5-di-O-(tert-butyldimethylsilyl)-D-ribofuranose | 950830-41-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1β-(6-chloropyridin-3-yl)-1,2-dideoxy-3,5-di-O-(tert-butyldimethylsilyl)-D-ribofuranose
• 英文别名: tert-butyl-[[(2R,3S,5R)-3-[tert-butyl(dimethyl)silyl]oxy-5-(6-chloropyridin-3-yl)oxolan-2-yl]methoxy]-dimethylsilane
• CAS: 950830-41-8
• 化学式: C₂₂H₄₀ClNO₃Si₂
• 分子量: 458.188
• InChiKey: NFDFLYCVVBWQNP-CEXWTWQISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.98
• 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：
  40.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1β-(6-chloropyridin-3-yl)-1,2-dideoxy-3,5-di-O-(tert-butyldimethylsilyl)-D-ribofuranose 在 palladium on activated charcoal 氢气 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 20.0 ℃ 、101.0 kPa 条件下， 反应 0.83h， 以82%的产率得到1β-(pyridin-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
• 作为产物：
  描述：

  {(2R,3S)-3-[(tert-butyldimethylsilyl)oxy]-2,3-dihydrofuran-2-yl}methanol 在 palladium diacetate 咪唑 、 三苯胂 、 三乙酰氧基硼氢化钠 、 溶剂黄146 、 triethylamine tris(hydrogen fluoride) 、 silver carbonate 作用下， 以 四氢呋喃 、 氯仿 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 16.16h， 生成 1β-(6-chloropyridin-3-yl)-1,2-dideoxy-3,5-di-O-(tert-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

• Synthesis of Phenol and Pyridone C-Ribo- and 2′-Deoxyribonucleosides by Palladium-Catalyzed Hydroxylations of Haloaryl C-Nucleosides
  作者：Michal Hocek、Martin Štefko

  DOI：10.1055/s-0030-1258318

  日期：2010.12

  Phenol and pyridone C-nucleosides in both ribo- and deoxyribo series were prepared by palladium-catalyzed hydroxylations reactions from the corresponding TBS-protected bromophenyl and bromo- or chloropyridyl C-nucleosides using Buchwald-type ligand under mild conditions. Partial or complete desilylation of 5′-OH was observed in some cases. Free nucleosides (7 examples) were obtained in good overall

  核糖和脱氧核糖系列中的苯酚和吡啶酮C-核苷是由钯催化的羟基化反应，由相应的TBS保护的溴苯基和溴或氯吡啶基C-核苷在温和条件下使用Buchwald型配体制备的。在某些情况下，观察到5'-OH的部分或完全甲硅烷基化。游离核苷（7个实施例）在由TBS保护基团用Et切割好的总产率得到3 N˙3HF。 C-核苷-钯催化-羟基化-苯酚-吡啶酮
• 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).