Density Functional Theory Study on the Mechanism of Nickel-Catalyzed 3,3-Dialkynylation of 2‑Aryl Acrylamides Via Double Vinylic C–H Bond Activation

The mechanisms of Ni-catalyzed 3,3-dialkynylation of 2-aryl acrylamide have been investigated by using density functional theory calculations. The result shows that this reaction includes double alkynylation, which involves sequential key steps of vinylic C–H bond activation, successive oxidative addition, and reductive elimination, with the second C–H bond activation being the rate-determining step. C–H and N–H bond activation occurs via the concerted metalation-deprotonation mechanism. The calculations show that no transition state exists in the first reductive elimination process, and a negative free energy barrier in the second reductive elimination process though a transition state is identified, indicating that the nickel-catalyzed vinylic C(sp²)–C(sp) bond formation does not require activation energy. Z–E isomerization is the prerequisite for the second alkynylation. In addition, our spin-flip TDDFT (SF-TDDFT) computational result discloses that the actual process of Z–E isomerization occurs on the potential energy surface of the first excited singlet state S₁.