Gold Redox Catalysis Enabled by Cyclic Diacyl Peroxides for Homocoupling and Cross-Coupling of Terminal Alkynes

Conjugated 1,3-diynes are valuable scaffolds, yet their selective assembly via cross-coupling of terminal alkynes remains challenging. In this study, we report a gold redox catalytic system employing cyclic diacyl peroxides as dual-function oxidants that enable both homocoupling and cross-coupling of terminal alkynes without exogenous ligands. This operationally simple protocol proceeds under mild conditions, exhibits broad substrate scope, and delivers symmetrical and unsymmetrical 1,3-diynes in moderate to good yields. The tether-guided redox platform facilitates efficient Au(I)/Au(III) redox cycling, offering a previously unrecognized catalytic paradigm to ligand-free gold catalysis for selective C(sp)─C(sp) bond formation.