Empirical and Computational Insights into N-Arylation Reactions Catalyzed by Palladium meta-Terarylphosphine Catalyst.

An in situ generated Pd-Cy*Phine catalyst has been successfully applied to the N-arylation of primary and secondary amines, and it exhibited high performance across multiple substrate classes. The performance induced by the meta-terarylphosphine motif of the Cy*Phine ligand for C-N cross-coupling displayed only subtle differences to that of its biarylphosphine congener XPhos. DFT studies demonstrated comparable reaction energetics in the catalytic cycle steps for both Pd-Cy*Phine and Pd-XPhos, which was consistent with previous findings. The computational investigation also indicated that a putative rate-determining step occurred after amine binding, which was likely to have annulled the expected benefits of having a meta-terarylphosphine ligand architecture.