Methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-3-C-(hydroxymethyl)-β-D-erythro-pentofuranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-3-C-(hydroxymethyl)-β-D-erythro-pentofuranoside
• 英文别名: (2R,3R,5R)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-3-(hydroxymethyl)-5-methoxyoxolan-3-ol
• 化学式: C₂₃H₃₂O₅Si
• 分子量: 416.59
• InChiKey: ABVNAKDGYUUORQ-MQSCRBSSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.05
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  68.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1-甲氧基-5-O-(叔丁基二苯基硅烷)-2-脱氧-beta-D-赤式戊呋喃糖苷 在 吡啶 、 chromium(VI) oxide 、 四氧化锇 、 水 、 乙酸酐 、 四氯化钛 、 N-甲基吗啉氧化物 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 6.25h， 生成 Methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-3-C-(hydroxymethyl)-β-D-erythro-pentofuranoside
  参考文献：
  名称：

  2-Deoxy-3-C-(hydroxymethyl)-D-pentofuranose Derivatives: Stereoselective Synthesis and Conversion into a Novel Class of Nucleoside Analogs

  摘要：

  Oxidation of pure anomers of 5-O-monoprotected methyl 2-deoxy-D-ribofuranosides 3-6 followed by Lombardo methylenation afforded the novel 3-C-methylene pentofuranosides 11-14. Subsequent osmium tetraoxide-catalyzed dihydroxylations of 11, 13, and 14 afforded a mixture of erythro- and three-configured S-C-hydroxymethyl furanosides 15/16, 18/19, and 20/21, respectively. However, analogous dihydroxylation of 5-O-(4-phenylbenzoyl)-protected beta-anomer 12 proceeded with complete stereoselectivity to give 3-C-(hydroxymethyl)-beta-D-erythro pentofuranoside 17 in 76% yield. Conversion of 17 to the corresponding primary tosylate 22, followed by base-catalyzed nucleophilic attack by the nucleobases adenine and thymine, afforded after deprotection compounds 25 and 26, respectively, as the first examples of a novel class of nucleoside analogues.

  DOI：

  10.1021/jo00127a041

文献信息

• 2-Deoxy-3-C-(hydroxymethyl)-D-pentofuranose Derivatives: Stereoselective Synthesis and Conversion into a Novel Class of Nucleoside Analogs
  作者：Claus Scheuer-Larsen、Henrik M. Pfundheller、Jesper Wengel

  DOI：10.1021/jo00127a041

  日期：1995.11

  Oxidation of pure anomers of 5-O-monoprotected methyl 2-deoxy-D-ribofuranosides 3-6 followed by Lombardo methylenation afforded the novel 3-C-methylene pentofuranosides 11-14. Subsequent osmium tetraoxide-catalyzed dihydroxylations of 11, 13, and 14 afforded a mixture of erythro- and three-configured S-C-hydroxymethyl furanosides 15/16, 18/19, and 20/21, respectively. However, analogous dihydroxylation of 5-O-(4-phenylbenzoyl)-protected beta-anomer 12 proceeded with complete stereoselectivity to give 3-C-(hydroxymethyl)-beta-D-erythro pentofuranoside 17 in 76% yield. Conversion of 17 to the corresponding primary tosylate 22, followed by base-catalyzed nucleophilic attack by the nucleobases adenine and thymine, afforded after deprotection compounds 25 and 26, respectively, as the first examples of a novel class of nucleoside analogues.