Predictable site-selective functionalization: Promoter group assisted <i>para</i>-halogenation of <i>N</i>-substituted <b>(</b>hetero<b>)</b>aromatics under metal-free condition
SEAr (electrophilic aromatic substitution) type reaction is disclosed. SEAr type reaction has been utilized for the C5-bromination of indolines (para-selective) with N-bromosuccinimide under metal and additive-free conditions in good to excellent yields. The developed methodology is also applicable for iodination and challenging chlorination. The pyrimidyl group is identified as a reactivity tuner
本文公开了通过 S E Ar(亲电芳族取代)型反应对N-嘧啶基(杂)芳烃进行区域选择性对-C-H 卤化。S E Ar 型反应已用于二氢吲哚的 C5-溴化(对位选择性)与N-溴代琥珀酰亚胺在无金属和无添加剂的条件下具有良好至极好的收率。所开发的方法也适用于碘化和具有挑战性的氯化。嘧啶基被确定为反应性调节剂,它也控制区域选择性。本方法也适用于苯胺、吡啶、吲哚、羟吲哚、吡唑、四氢喹啉、异喹啉和咔唑的选择性卤化。Fukui 亲核性和自然电荷图等 DFT 研究也支持观察到的p-选择性。标题化合物后官能化为相应的芳基化、烯化和二卤化产物是通过一锅两步的方式实现的。还对药物/天然分子(哈明、依托考昔、可乐定和氯唑沙宗)进行了后期 C-H 溴化,以证明所开发方案的适用性。
Amination of Phosphorodiamidate-Substituted Pyridines and Related <i>N</i>-Heterocycles with Magnesium Amides
The amination of various phosphorodiamidate-substituted pyridines, quinolines, and quinoxaline with magnesium amides R2NMgCl·LiCl proceeds at room temperature within 8 h. Several pharmaceutically active amines were suitable substrates for this amination procedure, and also the antihistaminic tripelennamine was prepared. Additionally, several heterocyclic phosphorodiamidates underwent directed ortho-metalation
各种二氨基磷酸酯基取代的吡啶,喹啉,并用镁酰胺喹喔啉的胺化- [R 2个8小时内于室温下NMgCl·LiCl前进。几种药物活性胺是用于该胺化程序的合适底物,并且还制备了抗组胺的三烯胺。另外,使用TMPMgCl·LiCl(TMP = 2,2,6,6-四甲基哌啶基)或TMP 2 Mg·2LiCl对几种杂环二氨基氨基磷酸酯进行定向邻位金属化(D o M),然后在胺化步骤之前进行亲电子官能化,导致邻官能化的胺化N-杂环。
Synthesis and Photophysical Study of Heteropolycyclic and Carbazole Motif: Nickel-Catalyzed Chelate-Assisted Cascade C–H Activations/Annulations
作者:Namrata Prusty、Shyam Kumar Banjare、Smruti Ranjan Mohanty、Tanmayee Nanda、Komal Yadav、Ponneri C. Ravikumar
DOI:10.1021/acs.orglett.1c03234
日期:2021.12.3
through sequential C–H bond activations has been described. Regioselective indole C2/C3 functionalization has been achieved in the presence of indole C7-H, which is quite challenging. In addition, this approach also gives easy access to building a heteropolycyclic motif through C6/C7 C–H functionalization of indoline. This methodology is not limited to aromatic internalalkynes as coupling partners; aliphatic
Cu-Catalyzed Direct C7 Sulfonylation of Indolines with Arylsulfonyl Chlorides
作者:Changlei Zhi、Qiuling Wang、Shuang Liu、Yuting Xue、Linlin Shi、Xinju Zhu、Xin-Qi Hao、Mao-Ping Song
DOI:10.1021/acs.joc.9b02954
日期:2020.1.17
sulfonylation of indolines with easily accessible sulfonyl chlorides has been realized under an air atmosphere via a chelation-assisted strategy. This protocol exhibits several unique characteristics, including broad substrate scope, good functionalgroup tolerance, and operational convenience, which enable a regioselectiveaccess to a variety of C-7 functionalized indoline scaffolds in moderate to good yields
A Cu(I)‐catalyzed regioselective cross‐dehydrogenativecoupling of indoline with a variety aryl and alkyl carboxylic acids is described. The divergent process for the oxygenation was achieved in satisfactory yields under additive free conditions, which provides an efficient strategy for the regioselective C7 functionalization of indolines using inexpensive copper catalyst. Oxygen as the sole oxidant