2,2-pentamethylene-5-nitro-5-(2-propenyl)-1,3-dioxane | 221284-87-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-pentamethylene-5-nitro-5-(2-propenyl)-1,3-dioxane
• 英文别名: 3-allyl-3-nitro-1,5-dioxaspiro[5.5]undecane；3-Nitro-3-prop-2-enyl-1,5-dioxaspiro[5.5]undecane
• CAS: 221284-87-3
• 化学式: C₁₂H₁₉NO₄
• 分子量: 241.287
• InChiKey: KALRNQBFNAIWLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  64.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,2-pentamethylene-5-nitro-5-(2-propenyl)-1,3-dioxane 在 aluminum amalgam 、 三乙胺 作用下， 以 四氢呋喃 、 丙醇 、 水 为溶剂， 反应 4.5h， 生成 7-oxa-1-azabicyclo[2.2.1]heptane-2-spiro-5'-(1',3'-dioxan)-2'-spiro-1"-cyclohexane
  参考文献：
  名称：

  由4-硝基-1-丁烯衍生物制备高度取代的7-氧杂-1-氮杂双环[2.2.1]庚烷。路线到多取代的哌啶

  摘要：

  易于从钯（0）催化的硝基烷烃的C-烯丙基化反应中获得的4-硝基-1-丁烯衍生物2在包括分子内的三个步骤中转化为高度取代的7-氧杂-1-氮杂双环[2.2.1]庚烷衍生物6 1,3-偶极环加成反应。6中N–O键的催化氢解提供了多取代的4-羟基哌啶。

  DOI：

  10.1016/s0040-4020(01)00021-7
• 作为产物：
  描述：

  乙酸烯丙酯 、 3-硝基-1,5-二氧杂螺[5.5]十一烷 在 bis-triphenylphosphine-palladium(II) chloride sodium methylate 、 三苯基膦 作用下， 以 甲醇 为溶剂， 反应 15.5h， 以75%的产率得到2,2-pentamethylene-5-nitro-5-(2-propenyl)-1,3-dioxane
  参考文献：
  名称：

  由4-硝基-1-丁烯衍生物制备高度取代的7-氧杂-1-氮杂双环[2.2.1]庚烷。路线到多取代的哌啶

  摘要：

  易于从钯（0）催化的硝基烷烃的C-烯丙基化反应中获得的4-硝基-1-丁烯衍生物2在包括分子内的三个步骤中转化为高度取代的7-氧杂-1-氮杂双环[2.2.1]庚烷衍生物6 1,3-偶极环加成反应。6中N–O键的催化氢解提供了多取代的4-羟基哌啶。

  DOI：

  10.1016/s0040-4020(01)00021-7

文献信息

• Synthesis, structure of 7-oxa-1-azabicyclo[2.2.1]heptane derivative obtained from sugar nitrone and analysis of its conformational variety
  作者：Tomasz Rowicki、Izabela D. Madura、Paulina H. Marek、Karolina Kopczyńska、Ewa Mironiuk-Puchalska、Wojciech Sas

  DOI：10.1016/j.molstruc.2019.01.058

  日期：2019.5

  N-(but-3-en-1-yl)nitrone 4. Structure of product 5 was attributed on the basis of NMR and X-ray analyses. In the solid state, three crystallographically independent molecules of 5 were detected, every exhibiting a different orientation of spiro connected rings. Conformational analysis performed by DFT calculations in the gas phase was performed and revealed that the conformations observed in the crystal

  摘要 7-氧杂-1-氮杂双环[2.2.1]庚烷5的二螺衍生物是由N-(5-烯丙基-螺[1,3-二恶烷-2,1'-环己烷]-5-的单一立体异构体合成的。基）羟胺 2 和受保护的 d-甘露糖 3，通过原位形成的 N-（but-3-en-1-yl）硝酮 4 的分子内 1,3-偶极环加成。产物 5 的结构基于 NMR和 X 射线分析。在固态下，检测到三个晶体学独立的 5 个分子，每个分子都表现出不同方向的螺连接环。在气相中通过 DFT 计算进行的构象分析表明，在晶体中观察到的构象对应于最稳定的分子几何形状。还发现其中两个在解决方案中占主导地位。
• Advanced Fine-Tuning of Grubbs/Hoveyda Olefin Metathesis Catalysts:  A Further Step toward an Optimum Balance between Antinomic Properties
  作者：Michał Bieniek、Robert Bujok、Maciej Cabaj、Noël Lugan、Guy Lavigne、Dieter Arlt、Karol Grela

  DOI：10.1021/ja063186w

  日期：2006.10.1

  A 95% yield in the cross metathesis of acrylonitrile with a model olefin is achieved at 25 degrees C with only 3 mol % of the new air-stable ruthenium catalyst 1f shown in the enclosed structural diagram. Even more remarkable are the performances of its boosted version 1g incorporating an electron-withdrawing group. Both these new enhanced versions of Hoveyda catalyst are readily available from Grubbs second generation precatalyst upon reaction with a styrenyl ether the end group of which has been functionalized by an ester function. The latter acts as a weakly coordinating ligand allowing to reach a desirable balance between antinomic properties such as the catalyst's stability, a high activity for challenging substrates, and a high initiation rate.
• Preparation of 2,2,6-trisubstituted 7-oxa-1-azabicyclo[2.2.1]heptanes from 4-nitro-1-butene derivatives. A route to 2,2,6-trisubstituted-4-hydroxypiperidines
  作者：Anna Budzińska、Maria Bukowska、Wojciech Sas

  DOI：10.1016/s0040-4039(98)02357-0

  日期：1999.1

  4-Nitro-1-butene derivatives 2 readily available from the palladium(0)-catalyzed C-allylation of nitroalkanes were converted into 7-oxa-1-azabicyclo[2.2.1]heptane derivatives 5 in three easy steps including an intramolecular 1,3-dipolar cycloaddition reaction of N-(3-alkenyl)nitrones. The palladium catalyzed hydrogenolysis of the compounds 5 afforded 2,2,6-trisubstituted-4-hydroxypiperidines The oxidation of 5 by 3 equiv. of m-chloroperbenzoic acid (MCPBA) gave acyclic beta-hydroxy-delta-nitroketones 9 in high yield. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Preparation of highly substituted 7-oxa-1-azabicyclo[2.2.1]heptanes from 4-nitro-1-butene derivatives. Route to polysubstituted piperidines
  作者：Anna Budzińska、Wojciech Sas

  DOI：10.1016/s0040-4020(01)00021-7

  日期：2001.3

  4-Nitro-1-butene derivatives 2 readily available from the palladium(0)-catalyzed C-allylation of nitroalkanes were converted into highly substituted 7-oxa-1-azabicyclo[2.2.1]heptane derivatives 6 in three steps including an intramolecular 1,3-dipolar cycloaddition reaction. Catalytic hydrogenolysis of the N–O bond in 6 afforded polysubstituted 4-hydroxypiperidines.

  易于从钯（0）催化的硝基烷烃的C-烯丙基化反应中获得的4-硝基-1-丁烯衍生物2在包括分子内的三个步骤中转化为高度取代的7-氧杂-1-氮杂双环[2.2.1]庚烷衍生物6 1,3-偶极环加成反应。6中N–O键的催化氢解提供了多取代的4-羟基哌啶。