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Exception to the ortho Effect in Palladium/Norbornene Catalysis
Author(s) -
Larraufie MarieHélène,
Maestri Giovanni,
Beaume Aurore,
Derat Étienne,
Ollivier Cyril,
Fensterbank Louis,
Courillon Christine,
Lacôte Emmanuel,
Catellani Marta,
Malacria Max
Publication year - 2011
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201104356
Subject(s) - palladium , norbornene , selectivity , catalysis , chemistry , chelation , computational chemistry , organic chemistry , monomer , polymer
Out of the norm : The first deviation from the ortho effect in palladium/norbornene catalysis, as evidenced by the resulting products, is reported (see scheme). DFT calculations indicate that this deviation is likely to originate from a distortion, caused by specific chelation, in the reductive‐elimination pathway from the Pd IV intermediate initially formed. Addition of water restores the normal selectivity, but also it leads to dearomatization.