Liu Ge, Ma Denghui, Zhang Jianchen, Yang Fanyuanhang, Gao Yuzhen, Su Weiping
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, PR China.
School of New Energy, Ningbo University of Technology, Ningbo, 315336, PR China.
Nat Commun. 2024 Nov 23;15(1):10153. doi: 10.1038/s41467-024-54239-5.
Photocatalytic N-to-C aryl migration allows for quick construction of highly useful amide derivatives from readily available compounds. By developing the reactions of sodium sulfinates with the N-aryl-propiolamides, we herein demonstrate that the CO-promoted visible-light-induced method enables a large variety of aryl groups on nitrogen atoms of the N-arylamides to undergo efficient aryl migration from N atom to C atom to synthesize tetra- and tri-substituted alkenyl amides selectively. 1,4-N-to-C aryl migration is a key step in this transformation which is achieved through photocatalytic radical-polar crossover pathway. The protocol exhibits the remarkably tolerant of the electronic properties of the migrating aryl substituent, as both electron-rich and -poor arenes are compatible with the migration process. As a result, this protocol features with a broad substrate scope, as demonstrated by more than 90 examples including complex bioactive compounds. Notably, abundant, nontoxic and low-cost CO acted as an essential and irreplaceable additive to enable the tetra- and tri-substituted alkenyl amides to be synthesized with excellent selectivity.
光催化氮到碳的芳基迁移能够从易得的化合物快速构建非常有用的酰胺衍生物。通过开发亚磺酸钠与N-芳基丙炔酰胺的反应，我们在此证明，CO促进的可见光诱导方法能够使N-芳基酰胺氮原子上的多种芳基从N原子到C原子进行高效的芳基迁移，从而选择性地合成四取代和三取代的烯基酰胺。1,4-氮到碳的芳基迁移是这一转化的关键步骤，该步骤通过光催化自由基-极性交叉途径实现。该方法对迁移芳基取代基的电子性质具有显著的耐受性，因为富电子和缺电子芳烃都与迁移过程兼容。因此，该方法具有广泛的底物范围，90多个实例（包括复杂的生物活性化合物）证明了这一点。值得注意的是，丰富、无毒且低成本的CO作为一种必不可少且不可替代的添加剂，能够以优异的选择性合成四取代和三取代的烯基酰胺。
