Under indium Lewis acid catalysis, electron‐rich five‐membered heteroaryl electrophiles fused with/without a benzene ring were found to couple with amines to produce heteroarylamines with broad structural diversity. The heteroarylamine formation proceeds through the cleavage of a heteroaryl−OMe bond by the nucleophilic attack of the amine based on the nucleophilic aromatic substitution (S_NAr) reaction. In contrast to the corresponding traditional S_NAr amination, the present S_NAr‐based heteroaryl amination can be performed without relying on both heteroaryl electrophiles with electron‐withdrawing groups and nucleophilicity‐enhanced metal amides. High compatibility towards the functional groups such as NO₂, Br, I, CF₃, CN, CO₂Et, pyridyl, thiazolyl, C=C, and OH groups was observed, thus showing the practicality and reliability of this method. Mechanistic studies indicated that a carbon−indium bond is likely to be formed on the heteroaryl ring during the process.

中文翻译：

---

杂芳胺库：胺催化的烷氧基杂芳烃的铟催化亲核芳香取代

在铟路易斯酸催化下，与/不与苯环稠合的富电子五元杂芳基亲电试剂与胺偶合生成具有广泛结构多样性的杂芳基胺。通过基于亲核芳香取代（S胺的亲核攻击，通过杂芳基- OME键的裂解的杂芳基形成前进_Ñ AR）反应。与相应的传统S _N Ar胺形成对比，目前基于S _N Ar的杂芳基胺化反应无需依赖具有吸电子基团的杂芳基亲电子试剂和亲核性增强的金属酰胺。对NO ₂，Br，I，CF ₃等官能团的高度相容性观察到CN，CO ₂ Et，吡啶基，噻唑基，C = C和OH基团，从而表明该方法的实用性和可靠性。机理研究表明，在此过程中，杂芳基环上可能会形成碳-铟键。