biostudies-literatureZheng LStrategic Priority Research Program of the Chinese Academy of SciencesNational Key R&D Program of ChinaProgram of Shanghai Academic/Technology Research LeaderProgram of Shanghai Academic Research LeaderNational Natural Science Foundation of ChinaNational Key Research and Development Program of Chinae2409457https://www.ebi.ac.uk/biostudies/studies/S-EPMC11615762biostudies-literatureUnknown11(45)The transition metal-catalyzed direct coupling reactions involving electron-rich Fischer carbene species are largely underdeveloped and remain a big challenge. Here, a direct coupling reaction of azoles and azine N-oxides is reported with Fischer copper carbene species bearing an α-siloxy group i, which can be in situ generated from acylsilanes catalytically under photoirradiation and redox-neutral conditions. This coupling reaction between electron-rich α-siloxy Fischer Cu-carbene species with hard carbanion nucleophiles may undergo a bimetallic relay process, which is confirmed by the kinetic analysis and in situ NMR analysis. This reaction features mild conditions and remarkable heterocycle compatibility. Notably, this protocol tolerates a series of azole or azine N-oxide derivatives, iAdvanced science (Weinheim, Baden-Wurttemberg, Germany)Photoinduced Copper-Catalyzed Cross-Coupling of Acylsilanes with Heteroarenes via Bimetallic Relay.PMC11615762221012912021YFA1500200XDB0610000223712932217127723XD1424500Li YCWang PZheng LWu YfalsePhotoinduced Copper-Catalyzed Cross-Coupling of Acylsilanes with Heteroarenes via Bimetallic Relay.The transition metal-catalyzed direct coupling reactions involving electron-rich Fischer carbene species are largely underdeveloped and remain a big challenge. Here, a direct coupling reaction of azoles and azine N-oxides is reported with Fischer copper carbene species bearing an α-siloxy group i, which can be in situ generated from acylsilanes catalytically under photoirradiation and redox-neutral conditions. This coupling reaction between electron-rich α-siloxy Fischer Cu-carbene species with hard carbanion nucleophiles may undergo a bimetallic relay process, which is confirmed by the kinetic analysis and in situ NMR analysis. This reaction features mild conditions and remarkable heterocycle compatibility. Notably, this protocol tolerates a series of azole or azine N-oxide derivatives, i2024-01-01T00:00:00Z2024 Dec2025-04-04T00:46:40.71Z2025-04-04T00:46:40.71ZS-EPMC116157623940140710.1002/advs.202409457