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Amination with Pd–NHC Complexes: Rate and Computational Studies on the Effects of the Oxidative Addition Partner
Author(s) -
Hoi Ka Hou,
Çalimsiz Selçuk,
Froese Robert D. J.,
Hopkinson Alan C.,
Organ Michael G.
Publication year - 2011
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.201002988
Subject(s) - deprotonation , carbene , amination , amine gas treating , chemistry , reactivity (psychology) , oxidative addition , oxidative phosphorylation , medicinal chemistry , catalysis , computational chemistry , combinatorial chemistry , organic chemistry , medicine , ion , biochemistry , alternative medicine , pathology
Pd‐PEPPSI‐IPent , a recently‐developed N‐heterocyclic carbene (NHC) complex, has been evaluated in amination reactions with secondary amines and it has shown superb reactivity under the most mildly basic reaction conditions. Rate and computational studies were conducted to provide insight into the mechanism of the transformation. The IPent catalyst coordinates to the amine much more strongly than the IPr variant, thus favouring deprotonation with comparatively weak bases. Indeed the reaction is first order in base and only slightly more than zeroth order in amine.