A palladium catalytic system incorporating novel Fc-JosiPhos ligands enables efficient C–N bond formation with diverse(hetero)aryl halides under low palladium loading(0.1 mol%).We rationally designed novel ferrocenyl...A palladium catalytic system incorporating novel Fc-JosiPhos ligands enables efficient C–N bond formation with diverse(hetero)aryl halides under low palladium loading(0.1 mol%).We rationally designed novel ferrocenyl phosphine-derived JosiPhos ligands(L1–L3).These ligands incorporate a ferrocenyl group providing greater steric bulk than tert-butyl or cyclohexyl and superior electron donation to cyclohexyl,along with a tunable side chain.They delivered excellent yields in the catalytic coupling of challenging(hetero)aryl chlorides with hydrazine.The scalable synthesis of arylhydrazines(5mmol scale)and subsequent cyclization to pyrazoles(65%–91%yields)highlights their potential for industrial conversion.Furthermore,the modularity of this strategy supports late-stage pharmaceutical functionalization,exemplified by TRPC inhibitor intermediate.展开更多
基金supported by the National Natural Science Foundation of China(2210829)We thank Analysis&Testing Laboratory for Life Sciences and Medicine of Air Force Medical University for HR MS analysis.
文摘A palladium catalytic system incorporating novel Fc-JosiPhos ligands enables efficient C–N bond formation with diverse(hetero)aryl halides under low palladium loading(0.1 mol%).We rationally designed novel ferrocenyl phosphine-derived JosiPhos ligands(L1–L3).These ligands incorporate a ferrocenyl group providing greater steric bulk than tert-butyl or cyclohexyl and superior electron donation to cyclohexyl,along with a tunable side chain.They delivered excellent yields in the catalytic coupling of challenging(hetero)aryl chlorides with hydrazine.The scalable synthesis of arylhydrazines(5mmol scale)and subsequent cyclization to pyrazoles(65%–91%yields)highlights their potential for industrial conversion.Furthermore,the modularity of this strategy supports late-stage pharmaceutical functionalization,exemplified by TRPC inhibitor intermediate.
