N-benzyl-1,2-O-isopropylidene-D-glyceraldehyde nitrone | 1165677-00-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-benzyl-1,2-O-isopropylidene-D-glyceraldehyde nitrone
• 英文别名: 2,3-O-isopropylidene-D-glyceraldehyde N-benzylnitrone；N-benzyl-1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]methanimine oxide
• CAS: 1165677-00-8
• 化学式: C₁₃H₁₇NO₃
• 分子量: 235.283
• InChiKey: SBWVZNCDVKIVPK-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  47.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-benzyl-1,2-O-isopropylidene-D-glyceraldehyde nitrone 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷-D2 为溶剂， 反应 0.08h， 生成 (3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-4-methoxy-3,6-dihydro-2H-1,2-oxazine
  参考文献：
  名称：

  烯丙基取代的羟胺环化成1,2-恶嗪的实验和计算研究

  摘要：

  动力学研究了烯丙基取代的羟胺向1,2-恶嗪的环化反应，揭示了ca的高一级同位素效应。6.7，低溶剂依赖性，对酸性或碱性添加剂的影响可忽略不计。DFT计算表明，作为关键中间体的两性离子中间体具有相当的稳定性，这也解释了观察到的微小碎片产物。

  DOI：

  10.1002/ejoc.202001147
• 作为产物：
  描述：

  (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-羧酸甲酯 在 二异丁基氢化铝 作用下， 生成 N-benzyl-1,2-O-isopropylidene-D-glyceraldehyde nitrone
  参考文献：
  名称：

  Diastereoselective synthesis of β-lactams via Kinugasa reaction of acyclic chiral nitrones

  摘要：

  An approach to beta-lactams via a Kinugasa reaction between chiral copper acetylides and chiral acyclic nitrones bearing either 1,3-dioxane or 1,3-dioxolane moieties is reported. The stereochemical preferences observed in these reactions are discussed. The reaction provides access to a variety of interesting beta-lactam structures. Electronic circular dichroism in combination with NMR spectroscopy was shown to be a useful and effective method for the reliable determination of the absolute configuration of all components of a complex mixtures of azetidinones. The effectiveness of the chiral analysis of complex mixtures was demonstrated for HPLC coupled on-line with electronic circular dichroism detection as well. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2015.11.006

文献信息

• OXAZOLIDIN-2-ONE COMPOUNDS AND USES THEREOF
  申请人：Novartis AG

  公开号：US20130225574A1

  公开（公告）日：2013-08-29

  The present invention relates to oxazolidin-2-one substituted pyrimidine compounds that act as PI3K (phosphatidylinositol-3-kinase) inhibitors, as well as pharmaceutical compositions thereof, methods for their manufacture and uses for the treatment of conditions, diseases and disorders dependent on PI3K.

  本发明涉及氧唑烷-2-酮取代嘧啶化合物，其作为PI3K（磷脂酰肌醇-3-激酶）抑制剂，以及其药物组合物、制备方法和用于治疗依赖于PI3K的疾病、病症和疾病的用途。
• Synthesis of Adamantylglycine Using a Diastereoselective Grignard-to-Nitrone Addition
  作者：Volker Jäger、Alevtina Baskakova、Wolfgang Frey

  DOI：10.1055/s-0030-1258235

  日期：2010.11

  tert-leucine, adamantylglycine has so far received little attention. Here, a new, practical synthesis of adamantylglycine is described. This is based on a highly diastereoselective addition of adamantyl Grignard reagent to 2,3-O-cyclohexylideneglyceraldehyde N-benzylnitrone, mediated by the Lewis acid diethylaluminum chloride. Adamantylglycine is obtained from the nitrone in 6 steps and 28% yield as

  与具有大取代基的氨基酸如叔亮氨酸相反，金刚烷基甘氨酸迄今为止很少受到关注。在此，描述了一种新的实用的金刚烷基甘氨酸合成方法。这是基于由路易斯酸二乙基氯化铝介导的将金刚烷基格利雅试剂高度非对映选择性地添加到2，3- O-环己基甘油醛N-苄基硝基。以6个步骤从硝酮获得金刚烷基甘氨酸，其为晶体盐酸盐的产率为28％，其中掺入0.5甲醇。 甘油醛-手性硝酮-格氏添加-亲电子甘氨酸当量-晶体结构
• Internally Protected Amino Sugar Equivalents from Enantiopure 1,2‐Oxazines: Synthesis of Variably Configured Carbohydrates with C‐Branched Amino Sugar Units
  作者：Fabian Pfrengle、Hans‐Ulrich Reissig

  DOI：10.1002/chem.201001060

  日期：2010.10.18

  precursors allowed the synthesis of homo‐oligomeric di‐ and trisaccharides 44, 46 and 47 or a hybrid trisaccharide 51 with natural carbohydrates. Access to a bivalent amino sugar derivative 54 was accomplished by reaction of rearrangement product 10 with 1,5‐pentanediol. Alternatively, when a protected L‐serine derivative was employed as glycosyl acceptor, the glycosylated amino acid 60 was efficiently prepared

  完成了立体构型合成不同构型的C2支链的4-氨基糖衍生物。路易斯酸介导的苯硫基取代的1,2-恶嗪的重排提供了可直接用于糖苷化反应的糖基供体等价物。甲醇处理内部提供保护的已转化成立体异构甲基糖苷氨基糖当量28，耳鼻喉科- 28，29，耳鼻喉科- 29和34在两个简单的还原步骤。与天然碳水化合物或双环氨基糖前体的反应可以合成同低聚二糖和三糖44，46和47或杂三糖51与天然碳水化合物。通过重排产物10与1,5-戊二醇的反应，可以得到二价氨基糖衍生物54。另外，当采用受保护的L-丝氨酸衍生物作为糖基受体时，只需几步即可有效地制备糖基化氨基酸60。在本报告中，我们描述了由对映体纯的1,2-恶嗪合成不寻常的氨基糖结构单元的方法，这些结构单元可以与天然碳水化合物或天然产物糖苷配基连接，以生产具有潜在化学药物用途的新的天然产物类似物。
• Synthesis of 1,2-Oxazinanes via Hydrogen Bond Mediated [3 + 3] Cycloaddition Reactions of Oxyallyl Cations with Nitrones
  作者：Lingbowei Hu、Michael Rombola、Viresh H. Rawal

  DOI：10.1021/acs.orglett.8b02301

  日期：2018.9.7

  the development of [3 + 3] cycloaddition reactions between oxyallyl cations and nitrones to yield 1,2-oxazinane heterocycles. Oxyallyl cation intermediates, generated in situ from α-tosyloxy ketones in the presence of hexafluoro-2-propanol (HFIP), a cosolvent, and a base, are found to react with a range of nitrones to afford 1,2-oxazinanes in good to high yields. The reactions are catalyzed by hydrogen-bond

  本文报道了在氧烯丙基阳离子和硝酮之间[3 + 3]环加成反应的发展，以产生1,2-恶嗪烷杂环。发现在六氟-2-丙醇（HFIP），助溶剂和碱的存在下，由α-甲苯磺酰氧基酮原位生成的草酸烯丙基阳离子中间体可与多种硝酮反应，从而提供良好的1,2-恶嗪二酮高产。该反应由氢键供体（例如苯酚和方酸酰胺）催化，观察到4-硝基苯酚的非对映选择性大大提高。
• Aza-Henry Reaction with Nitrones, an Under-Explored Transformation
  作者：Gatien Messire、Fabien Massicot、Alexis Vallée、Jean-Luc Vasse、Jean-Bernard Behr

  DOI：10.1002/ejoc.201801823

  日期：2019.2.21

  Comprehensive study of the addition of nitroalkanes to nitrones was conducted. The reaction proved efficient with TMAF or TBD as bases, in the presence of a large excess of R–NO2. Phase‐transfer catalysis gave also acceptable yields. Nitroethane or nitropropane afforded mixtures of isomerisable diastereomers. The reaction was applied to the synthesis of biologically relevant compounds.

  进行了将硝基烷烃添加到硝酮中的综合研究。在大量过量的R–NO 2的存在下，以TMAF或TBD为碱，该反应被证明是有效的。相转移催化也得到可接受的产率。硝基乙烷或硝基丙烷提供可异构的非对映异构体的混合物。该反应被用于生物相关化合物的合成。