4,4-dimethyl-3-phenyl-5-(((2,2,6,6-tetramethylpiperidin-1-yl)oxy)methyl)-4,5-dihydroisoxazole | 1403477-91-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 4,4-dimethyl-3-phenyl-5-(((2,2,6,6-tetramethylpiperidin-1-yl)oxy)methyl)-4,5-dihydroisoxazole
• 英文别名: 4,4-Dimethyl-3-phenyl-5-(((2,2,6,6-tetramethylpiperidin-1-yl)oxy)methyl)-4,5-dihydroisoxazole；4,4-dimethyl-3-phenyl-5-[(2,2,6,6-tetramethylpiperidin-1-yl)oxymethyl]-5H-1,2-oxazole
• CAS: 1403477-91-7
• 化学式: C₂₁H₃₂N₂O₂
• 分子量: 344.497
• InChiKey: KXIISTBIFKYKES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2,2-二甲基-1-苯基-丁-3-烯-1-醇 在 叔丁基过氧化氢 、 Jones reagent 、 五甲基二乙烯三胺 、 盐酸羟胺 、 sodium acetate 、 copper(l) cyanide 作用下， 以 乙醚 、 乙醇 、 水 、 乙腈 为溶剂， 反应 13.0h， 生成 4,4-dimethyl-3-phenyl-5-(((2,2,6,6-tetramethylpiperidin-1-yl)oxy)methyl)-4,5-dihydroisoxazole
  参考文献：
  名称：

  亚胺基自由基促进的未活化烯烃的氧氰化和氨基氰化：氰基异恶唑啉和环硝基的合成

  摘要：

  开发了一种新颖且简便的方法，用于内部未活化烯烃的邻位氧氰化和氨基氰化。该方法利用源自β，γ-和γ，δ-不饱和酮肟引发的亚氨基氧基的二分反应性，以叔丁基过氧化氢（TBHP）为环境友好型氧化剂，CuCN为氧化剂，提供内部烯烃的一般双官能化。市售的氰化试剂，以及五甲基二亚乙基三胺（PMDETA）作为配体。通过使用此协议，有效地制备了一系列有用的氰基特征的异恶唑啉和环状硝酮。

  DOI：

  10.1021/acs.orglett.7b00826

文献信息

• Oxime Radical Promoted Dioxygenation, Oxyamination, and Diamination of Alkenes: Synthesis of Isoxazolines and Cyclic Nitrones
  作者：Bing Han、Xiu-Long Yang、Ran Fang、Wei Yu、Chao Wang、Xiao-Yong Duan、Shuai Liu

  DOI：10.1002/anie.201203799

  日期：2012.8.27

  Up the tempo: The intramolecular addition of oxime radicals to CC bonds was achieved by using DEAD and TEMPO to give 4,5‐dihydroisoxazoles as a result of a CO bond‐forming, 5‐exo‐trig cyclization. γ,δ‐Unsaturated ketoximes also reacted to afford cyclic nitrones through CN bond formation. The reactions offer a metal‐free approach for the vicinal difunctionalization of unactivated alkenes.

  出速度：分子内除了肟基团到CC键的通过使用DEAD和TEMPO，得到4,5- dihydroisoxazoles作为结果实现一个C  O键形成，5-外-trig环化。γ，δ不饱和酮肟也反应至C，得到环状硝酮 N键的形成。这些反应为未活化烯烃的邻位双官能化提供了一种无金属的方法。
• Synthetic access to isoxazoline-functionalized isoquinolines <i>via</i> microwave-assisted iminoxyl radical-participated cascade cyclization of vinyl isocyanides
  作者：Yulong Xu、Hao Chen、Wei Li、Qiong Xie、Linqian Yu、Liming Shao

  DOI：10.1039/c8ob01229f

  日期：——

  A convenient microwave-assisted method for the synthesis of isoxazoline-functionalized isoquinolines via the n-Bu4NI (TBAI) catalyzed radical cascade cyclization of vinyl isocyanides with β,γ-unsaturated ketoximes has been described. The methodology presented here achieves a wide substrate scope and good to excellent yields. A radical mechanism is proposed, which is supported by the intermolecular

  为异恶唑啉官能化的异喹啉的合成中的方便微波辅助方法经由所述Ñ -Bu 4 NI（TBAI）与β乙烯基异氰化物的催化自由基级联环化，γ不饱和酮肟进行了说明。此处介绍的方法可实现较宽的基板范围，并具有良好的良率。提出了一种自由基机理，并由分子间竞争动力学同位素效应（KIE）实验和自由基俘获实验提供了支持。
• Cu-Catalyzed Oxyalkynylation and Aminoalkynylation of Unactivated Alkenes: Synthesis of Alkynyl-Featured Isoxazolines and Cyclic Nitrones
  作者：Wen-Jun Han、Yuan-Rui Wang、Jian-Wu Zhang、Fei Chen、Bo Zhou、Bing Han

  DOI：10.1021/acs.orglett.8b01004

  日期：2018.5.18

  oxyalkynylation/aminoalkynylation of internal unactivated alkenes is achieved by means of a Cu-catalyzed radical cascade reaction of unsaturated ketoximes with ethynylbenziodoxolone (EBX) reagents. This protocol enables the synthesis of structurally valuable isoxazolines or cyclic nitrones and the introduction of an important alkyne group in a single operation. The reaction is characterized by a broad substrate scope

  通过不饱和酮肟与乙炔基苯并恶唑啉酮（EBX）试剂的Cu催化自由基级联反应，可实现内部未活化烯烃的便捷，有效的邻位羰基化/氨基炔基化。该协议能够在一次操作中合成结构上有价值的异恶唑啉或环状硝酮，并引入重要的炔基。该反应的特征在于不饱和酮肟和炔基化试剂的底物范围宽，催化剂负载量低。
• Synthesis of Isoxazoline-Functionalized Phenanthridines via Iminoxyl Radical-Participated Cascade Sequence
  作者：Xiu-Long Yang、Fei Chen、Neng-Neng Zhou、Wei Yu、Bing Han

  DOI：10.1021/ol503335k

  日期：2014.12.19

  Readily accessible β,γ-unsaturated ketoximes reacted with 2-arylphenylisonitriles under the conditions of t-BuOOH and n-Bu4NI to give isoxazoline functionalized phenanthridines via tandem intramolecular/intermolecular C–O/C–C/C–C bond formation. The reaction involves the initial generation of iminoxyl radicals from the oxidation of β,γ-unsaturated ketoximes by t-BuOOH and n-Bu4NI followed a cascade

  容易获得β，γ不饱和酮肟与2- arylphenylisonitriles的条件下反应吨-BuOOH和Ñ -Bu 4 NI，得到异恶唑啉通过串联的分子内/分子间C-O / C-C / C-C键形成官能化菲啶。该反应通过涉及从β，γ不饱和酮肟的氧化初始产生iminoxyl自由基吨-BuOOH和Ñ -Bu 4 NI随后级联自由基环化/添加/环化序列。
• Iminoxyl Radical-Promoted Dichotomous Cyclizations: Efficient Oxyoximation and Aminooximation of Alkenes
  作者：Xie-Xue Peng、Yun-Jing Deng、Xiu-Long Yang、Lin Zhang、Wei Yu、Bing Han

  DOI：10.1021/ol502258n

  日期：2014.9.5

  A novel iminoxyl radical-involved metal-free approach to vicinal oxyoximation and aminooximation of unactivated alkenes is developed. This method utilizes the dichotomous reactivity of the iminoxyl radical to furnish a general difunctionalization on alkenes using simple tert-butyl nitrite (TBN) as the iminoxyl radical initiator as well the carbon radical trap. By using this protocol, oxime featured 4,5-dihydroisoxazoles and cyclic nitrones were facilely prepared from beta,gamma- and gamma,delta-unsaturated ketoximes, respectively.