Direct arene C−H functionalization via nucleophilic aromatic substitution remains a challenging task. Here we report an iridium nitrenoid-catalysed arene C−H functionalization strategy, making use of readily available aryl azides as electrophiles to react with different nucleophilic reaction partners. The practicality of this methodology is demonstrated by enantioselective synthesis of chiral 2-amino-2′-hydroxy-1,1′-binaphthyl, a class of building blocks, ligands and catalysts in asymmetric transformation, using β-naphthols and β-naphthyl azides as starting materials under the catalysis of a tailored oxazoline-chelated iridium complex. Mechanistic studies and density functional theory calculations show that the reaction proceeds through an iridium nitrenoid-mediated C−H functionalization pathway. The reported arene C−H functionalization strategy serves as a blueprint to expand the applicability of nucleophilic aromatic substitution reactions and is particularly valuable for the synthesis of aniline-containing molecules.

通过亲核芳香取代直接芳烃 C−H 官能化仍然是一项具有挑战性的任务。在这里，我们报告了一种铱氮烯基催化芳烃 C−H 官能化策略，利用容易获得的芳基叠氮化物作为亲电子试剂与不同的亲核反应伙伴发生反应。使用 β-萘酚和 β-萘基叠氮化物对映选择性合成手性 2-氨基-2'-羟基-1,1'-联萘（一类不对称转化中的结构单元、配体和催化剂）证明了该方法的实用性在定制的恶唑啉螯合铱络合物的催化下作为起始材料。机理研究和密度泛函理论计算表明，该反应通过铱氮介导的 C−H 官能化途径进行。报道的芳烃CH官能化策略可以作为扩展亲核芳香取代反应的适用性的蓝图，对于含苯胺分子的合成特别有价值。