Integrated nickel/polymer dual catalytic system for visible-light-driven sulfonamidation between aryl halides and aryl sulfonamides

By merging transition metal and heterogeneous photocatalyst, a metal-photoredox system has attracted more attention for cross-coupling of various dual photoredox catalysis. However, there is a grand challenge for the attenuated nucleophilicity of sulfonamides relative to alkyl amines. Herein, an integrated dual catalytic system of porous carbon nitride nanosheet with nitrogen vacancies (N V -P-C 3 N 4 ) as a conjugated polymer semiconductor host in combination with transition-metal nickel (Ni) was constructed by a defect and morphology regulation strategy toward visible-light-driven sulfonamidation between aryl halides and aryl sulfonamides. The excellent nickel/photoredox-catalyzed C–N coupling reaction performance is ascribed to the large specific surface area, abundant active sites, long carrier lifetime, and efficient transfer and separation of photoexcited electrons and holes. This work highlights the opportunity to cooperate with heterogeneous catalysts and active metal sites for challenging cross-coupling reactions. • Dual catalytic system of photoredox and transition metal • Carbon nitride with defect and morphology characteristics • C–N cross-coupling • Heterogeneous catalysts are used for sulfonamidation reactions For the fine chemical and pharmaceutical synthesis communities, it is crucial to determine the formation of anilines through C–N bond transformation approach. Considerable progress has been reported on dual catalytic systems of homogeneous photocatalysts combined with transition metals. However, the progress of heterogeneous catalysts for dual catalysis has not been satisfactory. Carbon nitride (C 3 N 4 ) is a class of metal-free conjugated polymer semiconductor with great potential for photoredox/Ni dual catalytic cross-couplings due to its thermal and chemical stability, facile fabrication, and cheapness. Herein, porous carbon nitride nanosheets with nitrogen vacancies (N V -P-C 3 N 4 ) were fabricated by a defect and morphology regulation strategy for visible-light-driven sulfonamidation between aryl halides and aryl sulfonamides. This work highlights the opportunity to cooperate with heterogeneous catalysts and active metal sites for challenging cross-coupling reactions. An integrated dual catalytic system of N V -P-C 3 N 4 in combination with transition-metal Ni was constructed toward visible-light-driven sulfonamidation between aryl halides and aryl sulfonamides. This work not only realizes the sulfonamidation reaction in a heterogeneous catalytic system for the first time but also demonstrates that defect engineering and morphology strategies are effective for enhancing photoredox dual catalytic performance.