2-(2-methylindolin-1-yl)-1H-benzo[d]imidazole | 1332624-61-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2-(2-methylindolin-1-yl)-1H-benzo[d]imidazole
• 英文别名: 2-(2-methyl-2,3-dihydroindol-1-yl)-1H-benzimidazole
• CAS: 1332624-61-9
• 化学式: C₁₆H₁₅N₃
• 分子量: 249.315
• InChiKey: PTVKTHUCJAKRMN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  31.9
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(2-methylindolin-1-yl)-1H-benzo[d]imidazole 、 二苯基乙炔 在 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 氧气 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以80%的产率得到13-methyl-4,5-diphenyl-13,14-dihydrobenzo[4',5']imidazo[2',1':2,3][1,3]diazepino[6,7,1-hi]indole
  参考文献：
  名称：

  Rh(III)-Catalyzed [5 + 2] Oxidative Annulation of Cyclic Arylguanidines and Alkynes to 1,3-Benzodiazepines. A Striking Mechanistic Proposal from DFT

  摘要：

  A novel and mild Rh(III)-catalyzed [5 + 2] oxidative annulation between cyclic arylguanidines and alkynes efficiently affords 1,3-benzodiazepines (pentacyclic guanidines). The use of O-2 as the sole oxidant in place of commonly used metal oxidants such as AgOAc clearly improves the efficiency of the oxidative annulation process. The mechanism of the cycloaddition most likely involves the formation of an eight-membered rhodacycle. DFT calculations support a striking mechanistic proposal for the [5 + 2] oxidative annulation.

  DOI：

  10.1021/acs.orglett.9b00354
• 作为产物：
  描述：

  2-甲基吲哚啉 在 正丁基锂 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 2-(2-methylindolin-1-yl)-1H-benzo[d]imidazole
  参考文献：
  名称：

  Rh(III)-Catalyzed [5 + 2] Oxidative Annulation of Cyclic Arylguanidines and Alkynes to 1,3-Benzodiazepines. A Striking Mechanistic Proposal from DFT

  摘要：

  A novel and mild Rh(III)-catalyzed [5 + 2] oxidative annulation between cyclic arylguanidines and alkynes efficiently affords 1,3-benzodiazepines (pentacyclic guanidines). The use of O-2 as the sole oxidant in place of commonly used metal oxidants such as AgOAc clearly improves the efficiency of the oxidative annulation process. The mechanism of the cycloaddition most likely involves the formation of an eight-membered rhodacycle. DFT calculations support a striking mechanistic proposal for the [5 + 2] oxidative annulation.

  DOI：

  10.1021/acs.orglett.9b00354

文献信息

• Direct, Metal-Free Amination of Heterocyclic Amides/Ureas with NH-Heterocycles and N-Substituted Anilines in POCl₃
  作者：Xiaohu Deng、Armin Roessler、Ivana Brdar、Roger Faessler、Jiejun Wu、Zachary S. Sales、Neelakandha S. Mani

  DOI：10.1021/jo201425q

  日期：2011.10.21

  A POCl3-mediated, direct amination reaction of heterocyclic amides/ureas with NH-heterocycles or N-substituted anilines is described. Compared to the existing methods, this operationally simple protocol provides unique reactivity and functional group compatibility because of the metal-free, acidic reaction conditions. The yields are generally excellent.

  描述了POCl 3介导的杂环酰胺/脲与NH-杂环或N-取代的苯胺的直接胺化反应。与现有方法相比，该操作简单的协议由于无金属的酸性反应条件，提供了独特的反应性和官能团兼容性。产量通常是极好的。
• Assembly of fluorinated benzodiazepines <i>via</i> Rh(<scp>iii</scp>)-catalysed [5+2] annulation of <i>N</i>-benzo[<i>d</i>]imidazole indolines with 2,2-difluorovinyl tosylate
  作者：Fu-Xiaomin Liu、Weijie Chen、Lei Ma、Kui Cheng、Zhi Zhou、Wei Yi

  DOI：10.1039/d3nj01544k

  日期：——

  an unusual 1,2-regioselectivity for the chemodivergent construction of monofluorinated and gem-difluorinated benzodiazepines, which are defined as potent anti-tumor agents against different cancer cell lines. In general, this work provides a powerful complement to both C–H activation chemistry and anti-tumor lead discovery.

  在此，我们实现了一种高效且溶剂可调的Rh( III )催化的N-苯并[ d ]咪唑二氢吲哚与2,2-二氟乙烯基甲苯磺酸酯的[5+2]成环反应，该反应呈现出不寻常的1,2-区域选择性。单氟化和双氟化苯二氮卓类药物的化学发散结构，被定义为针对不同癌细胞系的有效抗肿瘤剂。总的来说，这项工作为 C-H 活化化学和抗肿瘤先导化合物的发现提供了强有力的补充。
• Rhodium(III)‐Catalyzed C7‐Spiroannulation of Indolines with Maleimides: Facile Access to Aza‐Spiromulticycles
  作者：Jinfang Zhao、Chao Pi、Yangjie Wu、Xiuling Cui

  DOI：10.1002/adsc.202301463

  日期：2024.4.23

  Herein, we report a chemo‐ and regioselective Rh‐catalyzed redox C7‐spiroannulation reaction of N‐benzo[d]imidazole indolines with maleimides, resulting in a series of N‐benzo[d]imidazole indoline fused azaspirocycles in up to 92% yield. The synthetic utility is demonstrated by the synthesis of highly functionalized nitrogen‐containing spiropolycyclic skeletons. The annulation reaction could also be performed with maleic esters and acrylates. The products were purified by simple filtration. The Rh catalyst can be recycled, and the reaction could be performed at gram‐scale using 0.5 mol% of catalyst, which makes this protocol potentially applicable in industry. Moreover, the efficient post‐modification of pharmaceutical molecules demonstrates its practicability.

  摘要我们在此报告了一种由 Rh 催化的 N-苯并[d]咪唑吲哚啉与马来酰亚胺的化学和区域选择性 C7-螺烷化反应，从而得到一系列 N-苯并[d]咪唑吲哚啉融合的氮杂环，收率高达 92%。通过合成高度官能化的含氮双环骨架，证明了该合成方法的实用性。环化反应也可与马来酸酯和丙烯酸酯一起进行。产物可通过简单过滤进行纯化。Rh 催化剂可以循环使用，只需使用 0.5 摩尔%的催化剂就可以在克级规模上进行反应，这使得该方案有望应用于工业领域。此外，药物分子的高效后改性也证明了它的实用性。
• Rh(III)-Catalyzed [5 + 2] Oxidative Annulation of Cyclic Arylguanidines and Alkynes to 1,3-Benzodiazepines. A Striking Mechanistic Proposal from DFT
  作者：Nuria Martínez-Yáñez、Jaime Suárez、Ana Cajaraville、Jesús A. Varela、Carlos Saá

  DOI：10.1021/acs.orglett.9b00354

  日期：2019.3.15

  A novel and mild Rh(III)-catalyzed [5 + 2] oxidative annulation between cyclic arylguanidines and alkynes efficiently affords 1,3-benzodiazepines (pentacyclic guanidines). The use of O-2 as the sole oxidant in place of commonly used metal oxidants such as AgOAc clearly improves the efficiency of the oxidative annulation process. The mechanism of the cycloaddition most likely involves the formation of an eight-membered rhodacycle. DFT calculations support a striking mechanistic proposal for the [5 + 2] oxidative annulation.