Empirical and Computational Insights into N‐Arylation Reactions Catalyzed by Palladium meta‐Terarylphosphine Catalyst. Issue 5 (28th April 2017)

• Record Type: Journal Article
• Authors: Yong, Fui Fong; Mak, Adrian M.; Wu, Wenqin; Sullivan, Michael B.; Robins, Edward G.; Johannes, Charles W.; Jong, Howard; Lim, Yee Hwee
• Is Part Of: ChemPlusChem. Volume 82:Issue 5(2017)
• Page Start: 750
• Page End: 757
• Publication Date: 2017-04-28
• Subjects: amines -- arylation -- cross-coupling -- homogeneous catalysis -- palladium; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/cplu.201700042
• Languages: English
• ISSNs: 2192-6506

Abstract

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. Abstract : Get cross ! The Pd–Cy*Phine catalyst generated in situ was successfully applied to the N‐arylation cross‐coupling of primary and secondary amines (see figure), and it exhibits high performance across multiple substrate classes. Computational investigations also indicate that a putative rate‐determining step occurs after amine binding, which is likely to annul the expected benefits of the meta ‐terarylphosphine ligand architecture.