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Rhodium‐Complex‐Catalyzed Asymmetric Hydrogenation: Transformation of Precatalysts into Active Species
Author(s) -
Preetz Angelika,
Drexler HansJoachim,
Fischer Christian,
Dai Zhenya,
Börner Armin,
Baumann Wolfgang,
Spannenberg Anke,
Thede Richard,
Heller Detlef
Publication year - 2008
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.200701150
Subject(s) - rhodium , chemistry , catalysis , cyclooctadiene , cationic polymerization , olefin fiber , induction period , benzene , medicinal chemistry , asymmetric hydrogenation , organic chemistry , phenylphosphine , stoichiometry , enantioselective synthesis , phosphine
The use of diolefin‐containing rhodium precatalysts leads to induction periods in asymmetric hydrogenation of prochiral olefins. Consequently, the reaction rate increases in the beginning. The induction period is caused by the fact that some of the catalyst is blocked by the diolefin and thus not available for hydrogenation of the prochiral olefin. Therefore, the maximum reaction rate cannot be reached initially. Due to the relatively slow hydrogenation of cyclooctadiene (cod) the share of active catalysts increases at first, and this leads to typical induction periods. The aim of this work is to quantify the hydrogenation of the diolefins cyclooctadiene (cod) and norborna‐2,5‐diene (nbd) for cationic complexes of the type [Rh(ligand)(diolefin)]BF 4 for the ligands Binap (1,1′‐binaphthalene‐2,2′‐diylbis(phenylphosphine)), Me‐Duphos (1,2‐bis(2,5‐dimethylphospholano)benzene, and Catasium in the solvents methanol, THF, and propylene carbonate. Furthermore, an approach is presented to determine the desired rate constant and the resulting respective pre‐hydrogenation time from stoichiometric hydrogenations of the diolefin complexes via UV/Vis spectroscopy. This method is especially useful for very slow diolefin hydrogenations (e.g., cod hydrogenation with the ligands Me‐Duphos, Et‐Duphos (1,2‐bis(2,5‐diethylphospholano)benzene), and dppe (1,2‐bis(diphenylphosphino)ethane).