2,3-O-isopropylidene-1-O-methyl-5(R,S)-C-vinyl-β-D-ribofuranose | 327614-63-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-O-isopropylidene-1-O-methyl-5(R,S)-C-vinyl-β-D-ribofuranose
• CAS: 327614-63-1
• 化学式: C₁₁H₁₈O₅
• 分子量: 230.261
• InChiKey: IGQYZRUZDNQSBJ-BHRXDNSCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.42
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2,3-O-isopropylidene-1-O-methyl-5(R,S)-C-vinyl-β-D-ribofuranose 在 ammonium sulfate 、 硫酸 、 氨 、 溶剂黄146 、 六甲基二硅氮烷 、 三氟乙酸 、 锌 作用下， 以 吡啶 、 甲醇 、 水 、 溶剂黄146 、 间二甲苯 为溶剂， 反应 89.5h， 生成 4-amino-5-cyano-7-(5(S)-C-vinyl-β-D-ribofuranosyl)pyrrolo[2,3-d]pyrimidine
  参考文献：
  名称：

  Synthesis and cytotoxicity of 4′-C- and 5′-C-substituted toyocamycins

  摘要：

  Toyocamycin and some analogues have shown potent antitumor activities; however, none of them could be used clinically primarily owing to their cytotoxicity to normal human cells. In order to overcome the weakness of these nucleoside analogues, substitution of a variety of modified sugars for the ribofuranose was explored in our laboratories with expectation that certain sugar-modified toyocamycin analogues may be selectively cytotoxic to cancer cells. In this article, we report synthesis and cytotoxicity of 4'-C- and T-C-substituted toyocamycins, which were prepared via the condensations of 4-C- and 5-C-substituted ribofuranose derivatives 11, 12, 13, 20, 21, and 26 with the silylated form of 4-amino-6-bromo-5-cyanopyrrolo[2,3-d]py (27) and subsequent debromination and debenzoylation. When compared to the parent toyocamycin, all these analogues showed much lower cytotoxicity to human prostate cancer cells (HTB-81), mouse melanoma cancer cells (B16) as well as normal human fibroblasts. Compound le showed a significant cytotoxicity to the prostate cancer cells and a moderate selectivity. The results suggested that sugar modifications, especially those that may affect phosphorylation of nucleosides, could alter cytotoxicity profile significantly. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(00)00221-2
• 作为产物：
  描述：

  5(R,S)-C-ethynyl-2,3-O-isopropylidene-1-O-methyl-β-D-ribofuranose 在 nickel boride 氢气 、 乙二胺 作用下， 以 乙醇 为溶剂， 20.0 ℃ 、68.95 kPa 条件下， 反应 240.0h， 以63%的产率得到2,3-O-isopropylidene-1-O-methyl-5(R,S)-C-vinyl-β-D-ribofuranose
  参考文献：
  名称：

  Synthesis and cytotoxicity of 4′-C- and 5′-C-substituted toyocamycins

  摘要：

  Toyocamycin and some analogues have shown potent antitumor activities; however, none of them could be used clinically primarily owing to their cytotoxicity to normal human cells. In order to overcome the weakness of these nucleoside analogues, substitution of a variety of modified sugars for the ribofuranose was explored in our laboratories with expectation that certain sugar-modified toyocamycin analogues may be selectively cytotoxic to cancer cells. In this article, we report synthesis and cytotoxicity of 4'-C- and T-C-substituted toyocamycins, which were prepared via the condensations of 4-C- and 5-C-substituted ribofuranose derivatives 11, 12, 13, 20, 21, and 26 with the silylated form of 4-amino-6-bromo-5-cyanopyrrolo[2,3-d]py (27) and subsequent debromination and debenzoylation. When compared to the parent toyocamycin, all these analogues showed much lower cytotoxicity to human prostate cancer cells (HTB-81), mouse melanoma cancer cells (B16) as well as normal human fibroblasts. Compound le showed a significant cytotoxicity to the prostate cancer cells and a moderate selectivity. The results suggested that sugar modifications, especially those that may affect phosphorylation of nucleosides, could alter cytotoxicity profile significantly. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(00)00221-2

文献信息

• A Convenient and Versatile Method for the Preparation of α-Hydroxymethyl Ketone Derivatives from the Corresponding Allyl Silyl Ethers or Allyl Carboxylates
  作者：Yung-Son Hon、Ying-Chieh Wong、Kuo-Jui Wu

  DOI：10.1002/jccs.200800134

  日期：2008.8

  The ozonolysis of 1-substituted allyl silyl ethers or 1-substituted allyl carboxylates followed by treatment with bases gave the corresponding α-silyloxymethyl- or a-acyloxymethyl-ketones in good yields. It is proposed to proceed via the corresponding α-silyloxy- or α-acyloxyaldehydes intermediates followed by 1,4-group migration. The results of theoretical calculations are applicable to explain the

  1-取代的烯丙基甲硅烷基醚或1-取代的烯丙基羧酸盐随后用碱处理得到相应的α-甲硅烷氧基甲基-或α-酰氧基甲基-酮，产率良好。建议通过相应的 α-甲硅烷氧基或 α-酰氧基醛中间体进行，然后进行 1,4-基团迁移。理论计算结果适用于解释实验结果。
• Ring-closing metathesis strategy to unsaturated γ- and δ-lactones: Synthesis of hydroxyethylene isostere for protease inhibitors
  作者：Arun K. Ghosh、John Cappiello、Dongwoo Shin

  DOI：10.1016/s0040-4039(98)00887-9

  日期：1998.6

  acrylates derived from allylic and homo allylic alcohols in the presence of the Grubbs' catalyst (10–15 mol%) and titanium isopropoxide (0.3–3 equiv) provided ready access to α, β-unsaturated γ- and δ-lactones and an important dipeptide isostere intermediate.

  在Grubbs催化剂（10-15摩尔％）和异丙氧基钛（0.3-3当量）存在下，由烯丙基和均烯丙基醇衍生的丙烯酸酯的闭环烯烃复分解提供了现成的α，β-不饱和γ-和δ-内酯和重要的二肽等排中间体。
• Total Synthesis of Uracil Polyoxin C
  作者：Keisuke Kato

  DOI：10.1055/s-1998-4499

  日期：1998.10