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Unsymmetrical Bisphosphines for the Amidation of Aryl Chlorides: A Kinetic Study
Author(s) -
Falk Florian C.,
Oechsle Peter,
Thiel Werner R.,
Daniliuc ConstantinGabriel,
Paradies Jan
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201400159
Subject(s) - chemistry , transmetalation , reductive elimination , oxidative addition , aryl , moiety , palladium , phosphine , benzamide , ligand (biochemistry) , aryl halide , medicinal chemistry , isostructural , combinatorial chemistry , catalysis , organic chemistry , biochemistry , alkyl , receptor , crystal structure
Abstract The rate‐determining step of the palladium‐catalyzed amidation of 4‐chlorotoluene with benzamide in the presence of unsymmetrical bisphosphines was investigated. Isostructural [2.2]paracyclophane‐derived bisphosphines bearing dicyclohexylphosphino and diarylphosphino moieties were investigated as ligands in the oxidative addition and reductive elimination by kinetic studies. The reductive elimination was accelerated when a bisphosphine ligand was applied that contained an electron‐rich phosphine group and a less electron‐releasing phosphino moiety. Apart from the reductive elimination, the transmetallation had the largest impact on the palladium‐catalyzed amidation of aryl halides.