Mechanistic Discovery of a Nucleophile–Electrophile Coupling Mechanism in Binuclear Gold(I)-Catalyzed Photoredox Alkynylation of Tertiary Aliphatic Amines with 1-Iodoalkynes

Abstract

Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were employed to elucidate the mechanism of the α-amino-C(sp3)–H alkynylation of tertiary aliphatic amines with 1-iodoalkynes catalyzed by [Au2(μ-dppm)2]2+under light irradiation. TD-DFT results reveal that excitation proceeds via a metal-to-ligand charge-transfer (MLCT) transition involving low-lying π* orbitals of the dppm ligands rather than a metal-to-metal transition. The excited state oxidizes the amine substrate to generate an amine radical cation and a [AuI+ AuI]•+radical cation, with the latter acting as a strong reductant that transfers an electron to the C–I σ* orbital of 1-iodoalkyne, facilitating oxidative addition with an activation barrier of only 0.2 kcal/mol. The amine radical cation is deprotonated by a second amine, yielding an α-aminoalkyl radical. The resulting [AuI+ AuII(alkynyl)(I)]•+complex is then reduced by the α-aminoalkyl radical to produce an α-aminoalkyl carbocation and a linear Au(I)–alkynyl fragment. The alkynyl ligand subsequently attacks this carbocation in an outer-sphere nucleophile–electrophile coupling (NEC) step to form the C–C bond and regenerate the catalyst. This newly discovered NEC mechanism introduces unprecedented intermediates and provides a foundation for designing future transformations and addressing key mechanistic questions in the binuclear gold photoredox chemistry. Show more