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Empirical and Computational Insights into N‐Arylation Reactions Catalyzed by Palladium meta ‐Terarylphosphine Catalyst
Author(s) -
Yong Fui Fong,
Mak Adrian M.,
Wu Wenqin,
Sullivan Michael B.,
Robins Edward G.,
Johannes Charles W.,
Jong Howard,
Lim Yee Hwee
Publication year - 2017
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201700042
Subject(s) - catalysis , palladium , chemistry , catalytic cycle , congener , amine gas treating , ligand (biochemistry) , substrate (aquarium) , combinatorial chemistry , coupling reaction , computational chemistry , organic chemistry , biology , biochemistry , receptor , ecology
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.