1β-(6-aminopyridin-3-yl)-1-deoxy-2,3,5-tri-O-(tert-butyldimethylsilyl)-D-ribofuranose | 1315250-89-5

• 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-deoxy-2,3,5-tri-O-(tert-butyldimethylsilyl)-D-ribofuranose
• 英文别名: 5-[(2S,3S,4R,5R)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]pyridin-2-amine
• CAS: 1315250-89-5
• 化学式: C₂₈H₅₆N₂O₄Si₃
• 分子量: 569.02
• InChiKey: QUPWFOBRKXRDBP-WUEDSLEZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.91
• 重原子数：
  37
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  75.8
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1β-(6-aminopyridin-3-yl)-1-deoxy-2,3,5-tri-O-(tert-butyldimethylsilyl)-D-ribofuranose 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以65%的产率得到2-amino-5-(β-D-ribofuranosyl)pyridine
  参考文献：
  名称：

  General and Modular Synthesis of Isomeric 5-Substituted Pyridin-2-yl and 6-Substituted Pyridin-3-yl C-Ribonucleosides Bearing Diverse Alkyl, Aryl, Hetaryl, Amino, Carbamoyl, and Hydroxy Groups

  摘要：

  A general modular and practical methodology for preparation of diverse 5-substituted pyriclin-2-yl and 6-substituted pyridin-3-yl C-ribonucleosides was developed. Regioselective lithiation of 2,5-dibromopyridine proceeded at position 5 or 2 depending on the solvent, and the resulting bromopyridyl lithium species underwent additions to TBS-protected ribonolactone and follow-up transformations to corresponding acetylated hemiketal intermediates 7 and 10 that were diastereoselectively reduced to give either 5-bromopyridin-2-yl or 6-bromopyridin3-yl silyl-protected C-ribonucleosides 8 or 11 in 68% and 77% overall yields as pure beta-anomers. These bromopyridyl C-nucleoside intermediates were then subjected to a series of palladium-catalyzed cross-coupling reactions, aminations, aminocarbonylations, and hydroxylations to give a series of protected 1 beta-(5-alkyl-, 5-aryl-, 5-amino-, 5-carbamoyl-, and 5-hydroxypyridin-2-yl)-C-ribonucleosides 13a-i and beta-(6-alkyl-, 6-aryl-, 6-amino-, 6-carbamoyl-, and 6-hydroxypyridin-3-yl)-C-ribonucleosides 15a-i. Deprotection of silylated nucleosides by Et3N center dot 3HF, TBAF, or TFA gave a series of free C-nucleosides 14a-i and 16a-i.

  DOI：

  10.1021/jo200949c
• 作为产物：
  描述：

  2,3,5-tri-O-tert-butyldimethylsilyl-D-ribono-1,4-lactone 在 三乙基硅烷 、 tris-(dibenzylideneacetone)dipalladium(0) 、 正丁基锂 、 lithium hexamethyldisilazane 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.93h， 生成 1β-(6-aminopyridin-3-yl)-1-deoxy-2,3,5-tri-O-(tert-butyldimethylsilyl)-D-ribofuranose
  参考文献：
  名称：

  General and Modular Synthesis of Isomeric 5-Substituted Pyridin-2-yl and 6-Substituted Pyridin-3-yl C-Ribonucleosides Bearing Diverse Alkyl, Aryl, Hetaryl, Amino, Carbamoyl, and Hydroxy Groups

  摘要：

  A general modular and practical methodology for preparation of diverse 5-substituted pyriclin-2-yl and 6-substituted pyridin-3-yl C-ribonucleosides was developed. Regioselective lithiation of 2,5-dibromopyridine proceeded at position 5 or 2 depending on the solvent, and the resulting bromopyridyl lithium species underwent additions to TBS-protected ribonolactone and follow-up transformations to corresponding acetylated hemiketal intermediates 7 and 10 that were diastereoselectively reduced to give either 5-bromopyridin-2-yl or 6-bromopyridin3-yl silyl-protected C-ribonucleosides 8 or 11 in 68% and 77% overall yields as pure beta-anomers. These bromopyridyl C-nucleoside intermediates were then subjected to a series of palladium-catalyzed cross-coupling reactions, aminations, aminocarbonylations, and hydroxylations to give a series of protected 1 beta-(5-alkyl-, 5-aryl-, 5-amino-, 5-carbamoyl-, and 5-hydroxypyridin-2-yl)-C-ribonucleosides 13a-i and beta-(6-alkyl-, 6-aryl-, 6-amino-, 6-carbamoyl-, and 6-hydroxypyridin-3-yl)-C-ribonucleosides 15a-i. Deprotection of silylated nucleosides by Et3N center dot 3HF, TBAF, or TFA gave a series of free C-nucleosides 14a-i and 16a-i.

  DOI：

  10.1021/jo200949c

文献信息

• General and Modular Synthesis of Isomeric 5-Substituted Pyridin-2-yl and 6-Substituted Pyridin-3-yl <i>C</i>-Ribonucleosides Bearing Diverse Alkyl, Aryl, Hetaryl, Amino, Carbamoyl, and Hydroxy Groups
  作者：Martin Štefko、Lenka Slavětínská、Blanka Klepetářová、Michal Hocek

  DOI：10.1021/jo200949c

  日期：2011.8.19

  A general modular and practical methodology for preparation of diverse 5-substituted pyriclin-2-yl and 6-substituted pyridin-3-yl C-ribonucleosides was developed. Regioselective lithiation of 2,5-dibromopyridine proceeded at position 5 or 2 depending on the solvent, and the resulting bromopyridyl lithium species underwent additions to TBS-protected ribonolactone and follow-up transformations to corresponding acetylated hemiketal intermediates 7 and 10 that were diastereoselectively reduced to give either 5-bromopyridin-2-yl or 6-bromopyridin3-yl silyl-protected C-ribonucleosides 8 or 11 in 68% and 77% overall yields as pure beta-anomers. These bromopyridyl C-nucleoside intermediates were then subjected to a series of palladium-catalyzed cross-coupling reactions, aminations, aminocarbonylations, and hydroxylations to give a series of protected 1 beta-(5-alkyl-, 5-aryl-, 5-amino-, 5-carbamoyl-, and 5-hydroxypyridin-2-yl)-C-ribonucleosides 13a-i and beta-(6-alkyl-, 6-aryl-, 6-amino-, 6-carbamoyl-, and 6-hydroxypyridin-3-yl)-C-ribonucleosides 15a-i. Deprotection of silylated nucleosides by Et3N center dot 3HF, TBAF, or TFA gave a series of free C-nucleosides 14a-i and 16a-i.