Aryl amines are highly useful organic chemicals, but large-scale, transition-metal-free syntheses of aryl amines are surprisingly underdeveloped. A mild and scalable (up to 500 mmol) aryl amine synthesis from benzyne chemistry was invented using easily accessible aryl chlorides as precursors, NaH as a stoichiometric base, and a new type of sodium alkoxide cluster, X@RONa, as a catalyst. The cluster catalyst X@RONa featured an externally hydrophobic dodecameric sodium alkoxide shell housing an encapsulated center anion. The cluster made from methoxy-tert-butanol was found to be the most effective. The intramolecular version of this reaction allowed the synthesis of indolines and indoles. Experimental and computational mechanistic studies revealed that the rate-determining step was likely the transport of solid NaH into the X@RONa cluster in the organic phase.

中文翻译：

---

通过 X@RONa 催化苯炔形成从芳基氯可规模化无过渡金属合成芳基胺

芳基胺是非常有用的有机化学品，但令人惊讶的是，大规模、无过渡金属的芳基胺合成方法尚未开发。使用易于获得的芳基氯作为前体、NaH作为化学计量碱以及新型醇钠簇X@RONa作为催化剂，发明了一种温和且可规模化（高达 500 mmol）的苯炔化学合成芳基胺。簇催化剂X@RONa具有外部疏水的十二烷醇钠壳，其中包含封装的中心阴离子。发现由甲氧基叔丁醇制成的簇是最有效的。该反应的分子内形式可以合成二氢吲哚和吲哚。实验和计算机理研究表明，速率决定步骤可能是将固体 NaH 传输到有机相中的X@RONa簇中。