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Studies of Allylic Substitution Catalysed by a Palladium Complex of a C 2 ‐Symmetric Bis(aziridine): Preparation and NMR Spectroscopic Investigation of a Chiral π‐Allyl Species
Author(s) -
Andersson Pher G.,
Harden Adrian,
Tanner David,
Norrby PerOla
Publication year - 1995
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.19950010106
Subject(s) - aziridine , palladium , allylic rearrangement , moiety , chemistry , denticity , ligand (biochemistry) , stereochemistry , nuclear magnetic resonance spectroscopy , substitution reaction , catalysis , medicinal chemistry , crystallography , organic chemistry , ring (chemistry) , crystal structure , biochemistry , receptor
The chiral palladium π‐allyl intermediate for the catalytic asymmetric synthesis shown in Scheme 1 has been isolated as the PF − 6salt. MM 2 calculations have been performed and the structure of the palladium complex in solution has also been investigated by means of NMR spectroscopy. Both the computational and spectroscopic results suggest that in the complex the bidentate bis(aziridine) ligand adopts a conformation that forces the π‐allyl moiety out of the normally preferred square‐planar geometry. This nicely explains the very high enantioselectivity observed in the title reaction.