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Updated: Dec 30, 2025
Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Empirical and Computational Insights into N-Arylation Reactions Catalyzed by Palladium meta-Terarylphosphine Catalyst
Fui Fong Yong1, Adrian M Mak2, Wenqin Wu1
1Organic Chemistry, Institute of Chemical, Engineering Sciences (ICES), Agency for Science, Technology and Research (A*STAR), 8 Biomedical Grove, Neuros, #07-01, Singapore, 138665, Singapore.
Abstract:
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.
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