2-((3r,5r,7r)-adamantan-1-yl)-4H-benzo[d][1,3]oxazin-4-one | 1431097-82-3

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 2-((3r,5r,7r)-adamantan-1-yl)-4H-benzo[d][1,3]oxazin-4-one
• 英文别名: 2-(1-Adamantyl)-3,1-benzoxazin-4-one
• CAS: 1431097-82-3
• 化学式: C₁₈H₁₉NO₂
• 分子量: 281.354
• InChiKey: DFVUKBDCPWNPEE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  N-(2-iodobenzoyl)adamantane-1-carboxamide 在 potassium phosphate 、 copper(l) iodide 、 calcium chloride 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以61%的产率得到2-((3r,5r,7r)-adamantan-1-yl)-4H-benzo[d][1,3]oxazin-4-one
  参考文献：
  名称：

  Copper-Catalyzed C–N Bond Formation/Rearrangement Sequence: Synthesis of 4H-3,1-Benzoxazin-4-ones

  摘要：

  A facile and efficient copper-catalyzed method for the synthesis of 4H-3,1-benzoxazin-4-one derivatives has been developed. This procedure is based on a tandem intramolecular C-N coupling/rearrangement process. This method would provide a new and useful strategy for construction of N-heterocycles.

  DOI：

  10.1021/jo400515y

文献信息

• Palladium-Catalyzed Carbonylative Synthesis of Benzoxazinones from <i>N</i>-(<i>o</i>-Bromoaryl)amides Using Paraformaldehyde as the Carbonyl Source
  作者：Wanfang Li、Xiao-Feng Wu

  DOI：10.1021/jo5020118

  日期：2014.11.7

  Carbonylation reactions have been widely used in organic synthesis. However, the manipulation of toxic and pressurized carbon monoxide limited their applications in organic laboratories. The search for alternative carbonyl sources as an important method for carbonylative organic synthesis is spreading. Herein, a series of substituted benzoxazinones were synthesized from N-(o-bromoaryl)amides by palladium-catalyzed

  羰基化反应已广泛用于有机合成中。但是，有毒和加压一氧化碳的处理限制了它们在有机实验室中的应用。作为羰基化有机合成的重要方法，寻找替代的羰基来源的研究正在扩展。在此，由N-（邻-溴芳基）酰胺通过钯催化的羰基化，以低聚甲醛为羰基源，合成了一系列取代的苯并恶嗪酮，价格便宜，稳定且易于使用。值得注意的是，这是在钯催化的杂环羰基合成中使用多聚甲醛作为一氧化碳源的第一个例子。
• Selective Oxidative Decarbonylative Cleavage of Unstrained C(<i>sp</i>³)–C(<i>sp</i>²) Bond: Synthesis of Substituted Benzoxazinones
  作者：Ajay Verma、Sangit Kumar

  DOI：10.1021/acs.orglett.6b02142

  日期：2016.9.2

  A transition metal (TM)-free practical synthesis of biologically relevant benzoxazinones has been established via a selective oxidative decarbonylative cleavage of an unstrained C(sp3)–C(sp2) bond employing iodine, sodium bicarbonate, and tbutyl hydroperoxide in DMSO at 95 °C. Control experiments and Density Functional Theory (DFT) calculations suggest that the reaction involves a [1,5]H shift and

  通过使用碘，碳酸氢钠和叔丁基过氧化氢在DMSO中对未应变的C（sp 3）-C（sp 2）键进行选择性氧化脱羰裂解，建立了与生物相关的苯并恶嗪酮的无过渡金属（TM）实用合成方法在95°C下。控制实验和密度泛函理论（DFT）计算表明，该反应涉及[1,5] H转变和CO气体挤出作为关键步骤。还使用PMA–PdCl 2建立了CO的挤出。
• Pd‐Catalyzed Carbonylative Synthesis of 4 <i>H</i> ‐Benzo[ <i>d</i> ][1,3]Oxazin‐4‐Ones Using Benzene‐1,3,5‐Triyl Triformate as the CO Source
  作者：Yan Zheng、Mengke Dong、Erdong Qu、Jin Bai、Xiao‐Feng Wu、Wanfang Li

  DOI：10.1002/chem.202103137

  日期：2021.11.22

  A Pd-catalyzed CO-free carbonylative synthesis of 4H-benzo[d][1,3]oxazin-4-one derivatives was developed. This new method employed readily available N-(o-bromoaryl)amides as the starting materials and inexpensive benzene-1,3,5-triyl triformate (TFBen) as the stable solid CO surrogate, which would not cause hydrodehalogenation of the starting materials. Remarkably, this method featured a very broad

  开发了 Pd 催化的 4 H -benzo[ d ][1,3]oxazin-4-one 衍生物的无 CO 羰基化合成。这种新方法使用容易获得的N -（邻溴芳基）酰胺作为起始原料，使用廉价的三甲酸苯-1,3,5-三酯（TFBen）作为稳定的固体 CO 替代物，不会引起起始原料的加氢脱卤。值得注意的是，该方法具有非常广泛的底物范围，特别适用于将苯并[ d ][1,3]oxazin-4-one结构引入药物和天然生物活性化合物中。
• Silver and Palladium Cocatalyzed Carbonylative Activation of Benzotriazoles to Benzoxazinones under Neutral Conditions
  作者：Zhiping Yin、Zechao Wang、Xiao-Feng Wu

  DOI：10.1021/acs.orglett.7b03184

  日期：2017.11.17

  A novel and efficient method for the carbonylative activation of benzotriazoles to benzoxazinones has been developed. By using a silver and palladium bimetallic catalyst system, a broad range of benzotriazoles were transformed into the corresponding benzoxazinones in moderate to good yields with excellent functional group tolerance. Notably, this procedure proceeds under neutral conditions.

  已经开发出一种新颖有效的方法，用于苯并三唑羰基化活化为苯并恶嗪酮。通过使用银和钯双金属催化剂体系，各种苯并三唑以中等到良好的收率被转化为相应的苯并三嗪酮，并具有出色的官能团耐受性。值得注意的是，该过程在中性条件下进行。
• Palladium-Catalyzed Denitrogenative Carbonylation of Benzotriazoles with Cr(CO)₆ as the Carbonyl Source
  作者：Tongshun An、Chenwei Liu、Yanzhao Yin、Xiao-Feng Wu、Zhiping Yin

  DOI：10.1021/acs.organomet.2c00243

  日期：2022.7.11

  denitrogenative carbonylation of benzotriazoles for the synthesis of benzoxazin-4-ones has been developed. Employing benzotriazoles as easily accessible substrates and Cr(CO)6 as bench-stable solid carbonyl sources, various benzoxazin-4-ones were synthesized through a ring-opening/denitrogenative/carbonylation cascade processes in moderate to good yields. Notably, this protocol avoids the use of toxic CO gas and

  已经开发了用于合成苯并恶嗪-4-酮的通用钯和银共催化苯并三唑的脱氮羰基化。使用苯并三唑作为容易获得的底物和 Cr(CO) 6作为台式稳定的固体羰基源，通过开环/脱氮/羰基化级联过程以中等至良好的产率合成了各种苯并恶嗪-4-酮。值得注意的是，该协议避免了使用有毒 CO 气体和特殊设备，也可应用于从尿酸剂丙磺舒衍生的底物的后期功能化。