Methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-β-D-glycero-pentofuranosid-3-ulose | 172342-52-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-β-D-glycero-pentofuranosid-3-ulose
• 英文别名: (2R,5R)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-5-methoxyoxolan-3-one
• CAS: 172342-52-8
• 化学式: C₂₂H₂₈O₄Si
• 分子量: 384.547
• InChiKey: YOHIJGRNHGVONX-NHCUHLMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.89
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-β-D-glycero-pentofuranosid-3-ulose 在 吡啶 、 四氧化锇 、 水 、 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 6.0h， 生成 Methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-3-C-(hydroxymethyl)-β-D-threo-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
• 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 、 乙酸酐 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以89%的产率得到Methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-β-D-glycero-pentofuranosid-3-ulose
  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