CO2-promoted photocatalytic aryl migration from nitrogen to carbon for switchable transformation of N-arylpropiolamides
Ge Liu, Denghui Ma, Jianchen Zhang, Fanyuanhang Yang, Yuzhen Gao, Weiping Su
Abstract
Abstract 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 2 -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 2 acted as an essential and irreplaceable additive to enable the tetra - and tri -substituted alkenyl amides to be synthesized with excellent selectivity.