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Studies on the Amination of Aryl Chlorides with a Monoligated Palladium Catalyst: Kinetic Evidence for a Cooperative Mechanism
Author(s) -
Jimeno Ciril,
Christmann Ute,
EscuderoAdán Eduardo C.,
Vilar Ramon,
Pericàs Miquel A.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201202140
Subject(s) - amination , chemistry , catalysis , palladium , aryl , metalation , biphenyl , combinatorial chemistry , medicinal chemistry , stereochemistry , organic chemistry , alkyl
Combined spectroscopic, crystallographic, and kinetic studies of the mechanism of aromatic amination with the efficient dinuclear Pd precatalyst [Pd 2 Cl(μ‐Cl)P t Bu 2 (Bph‐Me)] (Bph‐Me=2′‐methyl‐[1,1′‐biphenyl]‐2‐yl) have revealed overlapping, yet cooperative, mechanistic scenarios, the relative weights of which are strongly influenced by the products formed as the reaction proceeds. The stability and evolution of the precatalyst in solution has been studied and several metalation pathways that point to a single monoligated intermediate have been identified. Our work sheds light on the nature of the catalytic species involved in the process and on the structure of the corresponding catalytic network.