[(3R,4S,5S)-4-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(iodomethyl)oxolan-3-yl] acetate | 201278-55-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: [(3R,4S,5S)-4-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(iodomethyl)oxolan-3-yl] acetate
• CAS: 201278-55-9
• 化学式: C₁₄H₂₇IO₄Si
• 分子量: 414.356
• InChiKey: PTDXPVIJDPVBAY-UPJWGTAASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.39
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 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：

  [(3R,4S,5S)-4-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(iodomethyl)oxolan-3-yl] acetate 在 氨 作用下， 以 甲醇 、 二甲基亚砜 为溶剂， 生成 (3R,4S,5S)-4-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(hydroxymethyl)oxolan-3-ol
  参考文献：
  名称：

  Synthesis and Testing of New Modified Nucleosides

  摘要：

  New efficient routes for the high-yielding synthesis of several classes of modified nucleosides have been developed. We have prepared both the D- and L-enantiomers of the methylene-expanded oxetanocin isonucleosides 1a-e and the L-2',3'-dideoxy isonucleosides 2abc (both the oxa and thia analgoues) as well as new routes for the preparation of L-ribose and 2-deoxy L-ribose 3ab and their modified nucleosides 4.

  DOI：

  10.1080/15257779908041490
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 吡啶 、 4-二甲氨基吡啶 、 bis(2,4,6-trimethylpyridine)silver(I) perchlorate 、 碘 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 35.0h， 生成 [(3R,4S,5S)-4-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(iodomethyl)oxolan-3-yl] acetate
  参考文献：
  名称：

  Synthesis of Methylene-Expanded Oxetanocin Isonucleosides in Both Enantiomeric Forms¹

  摘要：

  We report a novel route to isonucleosides of the 'methylene-expanded' oxetanocin class, in both the D-and L-enantiomeric forms, e.g., compounds L-(+)-2a, D-(-)-2a, and L-(-)-2b, beginning with the simple, known mono-p-bromobenzyl ether 3 of the very inexpensive 2-butene-1,4-diol. Sharpless asymmetric epoxidation of 3 gave either (-) or (+)-4 depending on the chirality of the tartrate used. The p-bromobenzyl ether was used since the epoxide product is crystalline and can be recrystallized to high optical purity. Opening of the epoxide with vinylmagnesium bromide gave the 1,3-diol 5, the primary alcohol of which was protected as the silyl ether 6. Treatment of 6 with iodonium bis(sym-collidine) perchlorate afforded the desired 5-(iodomethyl)tetrahydrofuran-3-ol 8 with loss of the bromobenzyl cation in the key step in the synthetic scheme. This iodide 8 was then converted into the bis(silyloxy)-protected alcohol 15 by acetylation to give the acetate 10, displacement of iodide with acetate, hydrolysis, and selective protection of the primary alcohols. The alcohol 6 could also be converted into 15 via initial acetylation and then iodocyclization to give 10. The diol 5 could also be converted into 15 by a similar route involving bis-acetylation and iodocyclization followed by functional group transformations. The tosylate of 15 was displaced with the anion of adenine or thymidine to give, alter final desilylation, the desired isonucleosides-the D-adenosine analogue (-)-2a and the L-adenosine and thymidine analogues (+)-2a and(-)-2b. All of the stereochemistry of the final products is derived from the first step of the synthesis, namely, the Sharpless asymmetric epoxidation of 3. The biological activity of the new compounds L-(+)-2a and L-(-)-2b against HIV was determined in the anti-HIV drug-testing system of the National Cancer Institute. The adenosine analogue L-(+)-2a was inactive in this screen, while the thymidine analogue L-(-)-2b showed moderate anti-HIV activity (IC50 > 2 x 10(-4) M, EC50 = 8 x 10(-7) M, TI50 > 250).

  DOI：

  10.1021/jo971890c