Bai Yaru, Jiang Hui-Mei, Xu Wenbo, Xu Li-Ping, Gao Hongyin
School of Chemistry and Chemical Engineering, Shandong University, 27 South Shanda Road, Ji'nan, 250100, Shandong, China.
School of Chemistry and Chemical Engineering, Ningxia University, 489 West Helanshan Road, Yinchuan, 750021, Ningxia, China.
Nat Commun. 2025 Sep 25;16(1):8399. doi: 10.1038/s41467-025-63534-8.
Due to the universality of arylamine and arylazide building blocks in pharmaceuticals, natural products and functional materials, the formation of aryl C-N bonds from readily available materials appears to be highly appealing, especially for the exclusive regioselective C-H amination. Despite substantial advancements in the synthesis of aryl C-N bonds, achieving a general, efficient, and para-selective C-H amination under mild conditions remains a significant challenge. Here we showcase a fluorosulfuryl imidazolium triflate-mediated para-selective C-H amination of N-arylhydroxylamines employing primary and secondary amines, diphenylmethanimine and azides as nitrogen source, affording structurally diverse 1,4-diaminoarenes or para-azidoanilides in the absence of oxidants and transition-metal catalysts. This effective protocol exhibits exclusive para-selectivity and good functional group tolerance for both N-arylhydroxylamines and N-nucleophiles (>90 examples). DFT calculations have been performed to elucidate the high chemoselectivity observed amidst multiple nucleophilic and electrophilic species.
由于芳胺和芳基叠氮砌块在药物、天然产物和功能材料中的普遍性，从易得的原料形成芳基C-N键显得极具吸引力，特别是对于专一的区域选择性C-H胺化反应。尽管芳基C-N键的合成取得了重大进展，但在温和条件下实现通用、高效和对位选择性的C-H胺化反应仍然是一项重大挑战。在此，我们展示了一种三氟甲磺酸氟磺酰亚胺介导的N-芳基羟胺与伯胺、仲胺、二苯甲亚胺和叠氮化物作为氮源的对位选择性C-H胺化反应，在无氧化剂和过渡金属催化剂的情况下，可得到结构多样的1,4-二氨基芳烃或对叠氮苯甲酰胺。该有效方法对N-芳基羟胺和N-亲核试剂均表现出专一的对位选择性和良好的官能团耐受性（>90个实例）。已进行密度泛函理论计算以阐明在多种亲核和亲电物种中观察到的高化学选择性。
