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Mechanistic Switch in Dual Gold Catalysis of Diynes: C(sp3)–H Activation through Bifurcation—Vinylidene versus Carbene Pathways


  • We thank Umicore AG & Co. KG for the generous donation of gold salts. M.M.H. is grateful to the Fonds der chemischen Industrie for a Chemiefonds scholarship and the Studienstiftung des deutschen Volkes. The computational studies were supported by bwGRiD, member of the German D-Grid initiative, funded by the Ministry for Education and Research (Bundesministerium für Bildung und Forschung) and the Ministry for Science, Research and Arts Baden-Württemberg.


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The other side of the mountain: Changing the framework of diyne systems opens up new cyclization modes for dual gold catalysis. Instead of a 5-endo cyclization and gold vinylidenes a 6-endo cyclization gives rise to gold-stabilized carbenes as key intermediates for selective C[BOND]H insertions.