Methyl 5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-3-C-methylene-α-D-glycero-pentofuranoside | 172293-90-2

• 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)-2,3-dideoxy-3-C-methylene-α-D-glycero-pentofuranoside
• 英文别名: tert-butyl-[[(2S,5S)-5-methoxy-3-methylideneoxolan-2-yl]methoxy]-diphenylsilane
• CAS: 172293-90-2
• 化学式: C₂₃H₃₀O₃Si
• 分子量: 382.575
• InChiKey: FRCPXBYTUUCDJX-YADHBBJMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.88
• 重原子数：
  27
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-3-C-methylene-α-D-glycero-pentofuranoside 在 吡啶 、 四氧化锇 、 水 、 N-甲基吗啉氧化物 作用下， 以 叔丁醇 为溶剂， 反应 5.0h， 生成 Methyl 5-O-(tert-butyldiphenylsilyl)-2-deoxy-3-C-(hydroxymethyl)-α-D-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：

  (2R,3S,5S)-2-tert-butyldiphenylsilanyloxymethyl-3-hydroxy-5α-methoxytetrahydrofuran 在 吡啶 、 chromium(VI) oxide 、 乙酸酐 、 四氯化钛 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.25h， 生成 Methyl 5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-3-C-methylene-α-D-glycero-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.