(Z)-2,3:5,6-di-O-isopropylidene-D-gulose oxime

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-2,3:5,6-di-O-isopropylidene-D-gulose oxime
• 英文别名: 2,3:5,6-O-diisopropylidene-D-gulose oxime；(S)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-[(4R,5S)-5-[(Z)-hydroxyiminomethyl]-2,2-dimethyl-1,3-dioxolan-4-yl]methanol
• 化学式: C₁₂H₂₁NO₆
• 分子量: 275.302
• InChiKey: GCYSHDWLKNPSBV-JMZXSEAPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  89.7
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (Z)-2,3:5,6-di-O-isopropylidene-D-gulose oxime 以 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 1.0h， 生成 N-[(3aR,4R,6S,6aR)-6-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-N-[(1R)-1-(1-benzothiophen-2-yl)ethyl]hydroxylamine
  参考文献：
  名称：

  Enantioselective synthesis of 5-LO inhibitors using a gulofuranose auxiliary

  摘要：

  The pure R-(+)-enantiomer of 5-lipoxygenase inhibitor Zileuton was prepared by diastereoselective methyl Grignard addition to an aldonitrone bearing a D-gulofuranose-derived chiral auxiliary. Addition of the Lewis acid trimethylaluminum leads to a reversal of the alkylation stereochemistry and the potent pyrido analogue, R-(+)-RS-27871 was prepared in this way from an L-gulofuranose-derived nitrone.

  DOI：

  10.1016/s0040-4039(00)79952-7
• 作为产物：
  描述：

  D-(-)-古洛糖酸-gamma-内酯 在 盐酸羟胺 、 二异丁基氢化铝 、 碳酸氢钠 、 对甲苯磺酸 作用下， 以 甲醇 、 水 、 丙酮 、 甲苯 为溶剂， 生成 (Z)-2,3:5,6-di-O-isopropylidene-D-gulose oxime
  参考文献：
  名称：

  Enantioselective synthesis of 5-LO inhibitors using a gulofuranose auxiliary

  摘要：

  The pure R-(+)-enantiomer of 5-lipoxygenase inhibitor Zileuton was prepared by diastereoselective methyl Grignard addition to an aldonitrone bearing a D-gulofuranose-derived chiral auxiliary. Addition of the Lewis acid trimethylaluminum leads to a reversal of the alkylation stereochemistry and the potent pyrido analogue, R-(+)-RS-27871 was prepared in this way from an L-gulofuranose-derived nitrone.

  DOI：

  10.1016/s0040-4039(00)79952-7

文献信息

• Reversal of Stereoselectivity in Cycloadditions of Five-Membered Cyclic Nitrones Derived from Hexoses
  作者：Tomáš Malatinský、Mária Spišáková、Matej Babjak、Jana Doháňošová、Jaromír Marek、Ján Moncol、Róbert Fischer

  DOI：10.1002/ejoc.201601488

  日期：2017.2.10

  Two five-membered cyclic nitrones derived from hexoses, a newly synthesized D-allo-configured nitrone and an already known D-talo-configured nitrone, have been examined in 1,3-dipolar cycloaddition reactions with vinyl acetate, allyl benzoate, methyl acrylate, acrylonitrile, and vinylene carbonate. The reactions of the D-allo-configured nitrone proceeded preferentially through the expected exo-anti

  已在与乙酸乙烯酯、苯甲酸烯丙酯、丙烯酸甲酯的 1,3-偶极环加成反应中研究了两种衍生自己糖的五元环硝酮、一种新合成的 D-allo-构型硝酮和一种已知的 D-talo-构型硝酮、丙烯腈和碳酸亚乙烯酯。D-allo-配置的硝酮的反应优先通过预期的外-反过渡态进行，但 D-talo-配置的硝酮的所有环加成令人惊讶地显示出高外-syn 选择性。这种立体选择性的逆转可以通过从 X 射线数据中获得的硝酮优选构象的 3D 分析来解释。使用 CONFLEX、PM5 和 DFT 计算进一步检查结构。
• Enantioselective, Chromatography-Free Synthesis of β³-Amino Acids with Natural and Unnatural Side Chains
  作者：Thibaud Gerfaud、Ying-Ling Chiang、Imants Kreituss、Justin A. Russak、Jeffrey W. Bode

  DOI：10.1021/op300069n

  日期：2012.4.20

  β3-Amino acids are key components of some pharmaceuticals, excellent surrogates for metabolically labile α-amino acids, and building blocks for chiral heterocycles. Unfortunately they are not easily accessible in enantiomerically pure form, especially when possessing unnatural side chains. A flexible, chromatography-free process for the synthesis of enantiopure β3-amino acids possessing natural and

  β 3 -氨基酸是一些药物的关键组分，代谢不稳定的α氨基酸优良替代物，和用于手性杂环积木。不幸的是，它们不容易以对映体纯的形式获得，特别是当具有不自然的侧链时。用于合成的柔性，自由色谱过程对映体纯β 3 -氨基酸具有天然和非天然侧链进行说明。该方法使用廉价的起始原料和试剂，为对映纯α-氨基酸的危险且昂贵的Arndt-Eistert同源提供了很好的替代方法。它的效用已被证明与两种有价值β制备规模合成3 -氨基酸具有非天然侧链。
• Enantioselective synthesis of 5-LO inhibitors using a gulofuranose auxiliary
  作者：John C. Rohloff、Thomas V. Alfredson、Martin A. Schwartz

  DOI：10.1016/s0040-4039(00)79952-7

  日期：1994.2

  The pure R-(+)-enantiomer of 5-lipoxygenase inhibitor Zileuton was prepared by diastereoselective methyl Grignard addition to an aldonitrone bearing a D-gulofuranose-derived chiral auxiliary. Addition of the Lewis acid trimethylaluminum leads to a reversal of the alkylation stereochemistry and the potent pyrido analogue, R-(+)-RS-27871 was prepared in this way from an L-gulofuranose-derived nitrone.