(1S,2R,3′S,4′S,5′S,2″R)-dispiro[(2-hydroxymethyl)cyclopentan-1,2′-(3′,4′-di-tert-butoxy)pyrrolidine-5′,1″-(2″-hydroxymethyl)cyclopentane]-1′-oxyl | 1412448-08-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (1S,2R,3′S,4′S,5′S,2″R)-dispiro[(2-hydroxymethyl)cyclopentan-1,2′-(3′,4′-di-tert-butoxy)pyrrolidine-5′,1″-(2″-hydroxymethyl)cyclopentane]-1′-oxyl
• CAS: 1412448-08-8
• 化学式: C₂₂H₄₀NO₅
• 分子量: 398.563
• InChiKey: UTZIPVPOTOYDSQ-ANWWMBAISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  63.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (3S,4S)-3,4-di-tert-butoxy-1-pyrroline N-oxide 在 titanium(IV) isopropylate 、 sodium tungstate 、 乙基溴化镁 、 双氧水 、 lead dioxide 、 magnesium 、 disodium ethylenediamine tetraacetic acid 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 乙醚 、 氯仿 、 水 、 甲苯 为溶剂， 反应 56.0h， 生成 (1S,2R,3′S,4′S,5′S,2″R)-dispiro[(2-hydroxymethyl)cyclopentan-1,2′-(3′,4′-di-tert-butoxy)pyrrolidine-5′,1″-(2″-hydroxymethyl)cyclopentane]-1′-oxyl
  参考文献：
  名称：

  通过组合的亲核加成和分子内的1,3-偶极环加成反应合成环状手性C 2对称的受阻位阻吡咯烷一氧化氮自由基

  摘要：

  位阻双螺环C 2对称手性吡咯烷型一氧化氮已成功地从1开始合成。-酒石酸衍生的硝酮。从两侧带有两个亚甲基的吡咯烷开始，两个α-碳原子的完全季铵化反应是通过重复进行完全区域和立体选择性分子内环加成反应以及将有机金属加成至关键的硝酮中间体而实现的，该过程依次由氧化过程形成。该方法似乎对于在氮氧化物基团附近建立大的螺环部分非常有用，并且为传统的氮氧化物合成方法提供了重要的补充。将合成的手性氨基氧表现出非常高的稳定性，以减少与抗坏血酸（ķ ≈8×10 -3中号-1小号-1）。

  DOI：

  10.1021/jo3019158

文献信息

• Synthesis of 1-azaspiro[4.4]nonan-1-oxyls via intramolecular 1,3-dipolar cycloaddition
  作者：Yulia V Khoroshunova、Denis A Morozov、Andrey I Taratayko、Polina D Gladkikh、Yuri I Glazachev、Igor A Kirilyuk

  DOI：10.3762/bjoc.15.200

  日期：——

  Sterically shielded nitroxides of the pyrrolidine series have shown the highest resistance to reduction. Here we report the synthesis of new pyrrolidine nitroxides from 5,5-dialkyl-1-pyrroline N-oxides via the introduction of a pent-4-enyl group to the nitrone carbon followed by an intramolecular 1,3-dipolar cycloaddition reaction and isoxazolidine ring opening. The kinetics of reduction of the new

  吡咯烷系列的立体屏蔽的氮氧化物显示出最高的抗还原性。在这里，我们报道了通过将5-戊烯基引入戊碳烯基，然后进行分子内1,3-偶极环加成反应和异恶唑烷，从5,5-二烷基-1-吡咯啉N-氧化物合成新的吡咯烷氮氧化物开环。研究了抗坏血酸还原新氮氧化物的动力学，并将其与先前发表的（1 S，2 R，3 'S，4 'S，5 'S，2″ R）-双螺[[2-羟甲基）环戊烷-1,2'-（3'，4'-二叔丁氧基）吡咯烷-5'，1''-（2''-羟甲基）环戊烷] -1'-氧基（1）。
• Room-temperature electron spin relaxation of nitroxides immobilized in trehalose: Effect of substituents adjacent to NO-group
  作者：Andrey A. Kuzhelev、Rodion K. Strizhakov、Olesya A. Krumkacheva、Yuliya F. Polienko、Denis A. Morozov、Georgiy Yu. Shevelev、Dmitrii V. Pyshnyi、Igor A. Kirilyuk、Matvey V. Fedin、Elena G. Bagryanskaya

  DOI：10.1016/j.jmr.2016.02.014

  日期：2016.5

  Trehalose has been recently promoted as efficient immobilizer of biomolecules for room-temperature EPR studies, including distance measurements between attached nitroxide spin labels. Generally, the structure of nitroxide influences the electron spin relaxation times, being crucial parameters for room-temperature pulse EPR measurements. Therefore, in this work we investigated a series of nitroxides with different substituents adjacent to NO-moiety including spirocyclohexane, spirocyclopentane, tetraethyl and tetramethyl groups. Electron spin relaxation times (T-1, T-m) of these radicals immobilized in trehalose were measured at room temperature at X- and Q-bands (9/34 GHz). In addition, a comparison was made with the corresponding relaxation times in nitroxide-labeled DNA immobilized in trehalose. In all cases phase memory times T-m, were close to 700 ns and did not essentially depend on structure of substituents. Comparison of temperature dependences of T-m at T = 80-300 K shows that the benefit of spirocyclohexane substituents well-known at medium temperatures (similar to 100-180 K) becomes negligible at 300 K. Therefore, unless there are specific interactions between spin labels and biomolecules, the room temperature value of T-m in trehalose is weakly dependent on the structure of substituents adjacent to NO-moiety of nitroxide. The issues of specific interactions and stability of nitroxide labels in biological media might be more important for room temperature pulsed dipolar EPR than differences in intrinsic spin relaxation of radicals. (C) 2016 Elsevier Inc. All rights reserved.
• Synthesis of a Chiral <i>C</i>₂-Symmetric Sterically Hindered Pyrrolidine Nitroxide Radical via Combined Iterative Nucleophilic Additions and Intramolecular 1,3-Dipolar Cycloadditions to Cyclic Nitrones
  作者：Denis A. Morozov、Igor A. Kirilyuk、Denis A. Komarov、Andrea Goti、Irina Yu. Bagryanskaya、Natalia V. Kuratieva、Igor A. Grigor’ev

  DOI：10.1021/jo3019158

  日期：2012.12.7

  successfully synthesized starting from an l-tartaric derived nitrone. Starting from a pyrrolidine flanked by two methylene groups, complete quaternization of the two α-carbon atoms has been accomplished through iteration of completely regio- and stereoselective intramolecular cycloaddition reactions and organometallic additions to key nitrone intermediates, formed in turn by oxidation procedures. This

  位阻双螺环C 2对称手性吡咯烷型一氧化氮已成功地从1开始合成。-酒石酸衍生的硝酮。从两侧带有两个亚甲基的吡咯烷开始，两个α-碳原子的完全季铵化反应是通过重复进行完全区域和立体选择性分子内环加成反应以及将有机金属加成至关键的硝酮中间体而实现的，该过程依次由氧化过程形成。该方法似乎对于在氮氧化物基团附近建立大的螺环部分非常有用，并且为传统的氮氧化物合成方法提供了重要的补充。将合成的手性氨基氧表现出非常高的稳定性，以减少与抗坏血酸（ķ ≈8×10 -3中号-1小号-1）。