1β-(6-bromopyridin-3-yl)-1-O-acetyl-2,3,5-tri-O-(tert-butyldimethylsilyl)-D-ribofuranose | 1315250-74-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1β-(6-bromopyridin-3-yl)-1-O-acetyl-2,3,5-tri-O-(tert-butyldimethylsilyl)-D-ribofuranose
• 英文别名: [(2R,3R,4R,5R)-2-(6-bromopyridin-3-yl)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl] acetate
• CAS: 1315250-74-8
• 化学式: C₃₀H₅₆BrNO₆Si₃
• 分子量: 690.938
• InChiKey: GELZRYJVGPGIMP-YOUOVVPYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.76
• 重原子数：
  41
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  76.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1β-(6-bromopyridin-3-yl)-1-O-acetyl-2,3,5-tri-O-(tert-butyldimethylsilyl)-D-ribofuranose 在 三乙基硅烷 、 四(三苯基膦)钯 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 2.16h， 生成 1β-(6-methylpyridin-3-yl)-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
• 作为产物：
  描述：

  2,5-二溴吡啶 、 乙酸酐 、 2,3,5-tri-O-tert-butyldimethylsilyl-D-ribono-1,4-lactone 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 0.77h， 以77%的产率得到1β-(6-bromopyridin-3-yl)-1-O-acetyl-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