N-(3,5-dimethylphenyl)-2-azetidinone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: N-(3,5-dimethylphenyl)-2-azetidinone
• 英文别名: 1-(3,5-dimethylphenyl)azetidin-2-one
• 化学式: C₁₁H₁₃NO
• 分子量: 175.23
• InChiKey: AXAFXAAVQKZCSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(3,5-dimethylphenyl)-2-azetidinone 在 三氟甲磺酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 2.0h， 生成 2,4-Dimethyl-5,6,7,8-tetrahydro-5-chinolinon
  参考文献：
  名称：

  通过[3+ + 2]-环加成/重排反应合成新的三环5,6-二氢-4H-苯并[b] [1,2,4]三唑并[1,5-d] [1,4]二氮杂衍生物。

  摘要：

  两个新的三环杂环系列，即5,6-二氢-4H-苯并[b] [1,2,4]三唑并[1,5-d] [1,4]二氮杂吡啶鎓盐10和相关的中性游离碱在原位的[3 ++ 2]-环加成反应中，在氯化铝存在下，由4-乙酰氧基-1-乙酰基-4-苯基偶氮-1,2,3,4-四氢喹啉8和腈9合成13。生成偶氮碳鎓中间体14，然后进行环扩环重排。在重排反应中，最初形成的螺-三唑鎓加合物16中的苯基取代基经历了[1,2]从C（3）迁移至电子不足的N（2）的过程。这导致环从6元哌啶扩环到7元二氮杂pine，提供了三环1,2,4-三唑稠合的1,4-苯并二氮杂s。

  DOI：

  10.3762/bjoc.14.155
• 作为产物：
  描述：

  3-bromo-N-(3,5-dimethylphenyl)propanamide 在 sodium t-butanolate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 N-(3,5-dimethylphenyl)-2-azetidinone
  参考文献：
  名称：

  通过[3+ + 2]-环加成/重排反应合成新的三环5,6-二氢-4H-苯并[b] [1,2,4]三唑并[1,5-d] [1,4]二氮杂衍生物。

  摘要：

  两个新的三环杂环系列，即5,6-二氢-4H-苯并[b] [1,2,4]三唑并[1,5-d] [1,4]二氮杂吡啶鎓盐10和相关的中性游离碱在原位的[3 ++ 2]-环加成反应中，在氯化铝存在下，由4-乙酰氧基-1-乙酰基-4-苯基偶氮-1,2,3,4-四氢喹啉8和腈9合成13。生成偶氮碳鎓中间体14，然后进行环扩环重排。在重排反应中，最初形成的螺-三唑鎓加合物16中的苯基取代基经历了[1,2]从C（3）迁移至电子不足的N（2）的过程。这导致环从6元哌啶扩环到7元二氮杂pine，提供了三环1,2,4-三唑稠合的1,4-苯并二氮杂s。

  DOI：

  10.3762/bjoc.14.155

文献信息

• Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds
  申请人：——

  公开号：US20030065187A1

  公开（公告）日：2003-04-03

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法。在某些实施例中，本发明涉及铜催化的方法，用于在酰胺或胺基团的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在酰基肼的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在另一些实施例中，本发明涉及铜催化的方法，用于在含氮杂环芳烃（例如吲哚、吡唑和吲哌）的氮原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氮键。在某些实施例中，本发明涉及铜催化的方法，用于在醇的氧原子与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-氧键。本发明还涉及铜催化的方法，用于在包含亲核碳原子的反应物（例如烯醇酸盐或丙二酸盐负离子）与芳基、杂原基或乙烯卤代物或磺酸酯的活化碳之间形成碳-碳键。重要的是，由于催化剂中铜的低成本，本发明的所有方法都相对廉价。
• A General and Efficient Copper Catalyst for the Amidation of Aryl Halides
  作者：Artis Klapars、Xiaohua Huang、Stephen L. Buchwald

  DOI：10.1021/ja0260465

  日期：2002.6.1

  was developed for the amidation of aryl halides by using 0.2-10 mol % of CuI, 5-20 mol % of a 1,2-diamine ligand, and K(3)PO(4), K(2)CO(3), or Cs(2)CO(3) as base. Catalyst systems based on N,N'-dimethylethylenediamine or trans-N,N'-dimethyl-1,2-cyclohexanediamine were found to be the most active even though several other 1,2-diamine ligands could be used in the easiest cases. Aryl iodides, bromides, and

  通过使用 0.2-10 mol% 的 CuI、5-20 mol% 的 1,2-二胺配体和 K(3)PO(4), K (2)CO(3) 或 Cs(2)CO(3) 作为碱。发现基于 N,N'-二甲基乙二胺或反式-N,N'-二甲基-1,2-环己二胺的催化剂体系是最活跃的，尽管在最简单的情况下可以使用其他几种 1,2-二胺配体。芳基碘化物、溴化物，在某些情况下甚至芳基氯化物都可以有效地酰胺化。反应中可以容忍多种官能团，包括许多与 Pd 催化的酰胺化或胺化方法不兼容的官能团。
• Copper-catalyzed formation of carbon heteroatom and carbon-carbon bonds
  申请人：Buchwald L. Stephen

  公开号：US20050215794A1

  公开（公告）日：2005-09-29

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法。在某些实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和酰胺或胺基团的氮原子之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和酰肼的氮原子之间形成碳-氮键。在其他实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和含氮杂环芳香族化合物（例如吲哚、吡唑和吲唑）的氮原子之间形成碳-氮键。在某些实施例中，本发明涉及铜催化的方法，用于在苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳和醇的氧原子之间形成碳-氧键。本发明还涉及铜催化的方法，用于在包含亲核碳原子（例如烯醇酸根离子或马隆酸根离子）的反应物和苯基、杂环基或乙烯基卤化物或磺酸盐的活性碳之间形成碳-碳键。重要的是，由于催化剂中铜的低成本，本发明的所有方法都相对廉价易行。
• Copper-catalyzed formation of carbon-heteroatom and carbon—carbon bonds
  申请人：Buchwald Stephen L.

  公开号：US09067955B2

  公开（公告）日：2015-06-30

  The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods, such as the reaction of Z-X with C(L)(R)(R′)2 in the present of a catalyst and a base, thereby forming C(Z)(R)(R′)2; wherein X represents I, Cl, alkylsulfonate, or arylsulfonate; Z represents optionally substituted aryl, heteroaryl or alkenyl; L represents H or a negative charge; catalyst comprises a copper atom or ion, and a ligand, wherein the ligand is an optionally substituted aryl alcohol, alkyl amine, 1,2-diamine, 1,2-aminoalcohol, 1,2-diol, imidazolium carbene, pyridine, or 1,10-phenanthroline; the ligand is a chelating ligand; and the base represents a Bronsted base; R represents H, optionally substituted alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl; R′ represents independently for each occurrence H, alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl, formyl, acyl, —CO2R″, —C(O)N(R)2, sulfonyl, —P(O)(OR″)2, —CN, or —NO2; R″ represents independently for each occurrence optionally substituted alkyl, cycloalkyl, aralkyl, aryl, or heteroaryl; and C(R′)2(R) taken together may represent nitrile.

  本发明涉及铜催化的碳-杂原子和碳-碳键形成方法，例如在催化剂和碱的存在下，Z-X与C（L）（R）（R'）2反应，从而形成C（Z）（R）（R'）2；其中X代表I，Cl，烷基磺酸盐或芳基磺酸盐；Z代表可选取代的芳基，杂原芳基或烯丙基；L代表H或负电荷；催化剂包括铜原子或离子和配体，其中配体是可选取代的芳基醇，烷基胺，1,2-二胺，1,2-氨基醇，1,2-二醇，咪唑卡宾，吡啶或1,10-菲啰啉；配体是螯合配体；碱代表布朗斯特德碱；R代表H，可选取代的烷基，环烷基，芳基烷基，芳基或杂原芳基；R'代表独立地为每个出现的H，烷基，环烷基，芳基烷基，芳基或杂原芳基，甲酰基，酰基，-CO2R″，-C（O）N（R）2，磺酰基，-P（O）（OR″）2，-CN或-NO2；R″代表独立地为每个出现的可选取代的烷基，环烷基，芳基烷基，芳基或杂原芳基；而C（R'）2（R）在一起可以代表腈。
• A General and Efficient Copper Catalyst for the Amidation of Aryl Halides and the <i>N</i>-Arylation of Nitrogen Heterocycles
  作者：Artis Klapars、Jon C. Antilla、Xiaohua Huang、Stephen L. Buchwald

  DOI：10.1021/ja016226z

  日期：2001.8.1