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Ir‐Catalysed Asymmetric Allylic Substitutions with Cyclometalated (Phosphoramidite)Ir Complexes—Resting States, Catalytically Active (π‐Allyl)Ir Complexes and Computational Exploration
Author(s) -
Raskatov Jevgenij A.,
Spiess Stephanie,
Gnamm Christian,
Brödner Kerstin,
Rominger Frank,
Helmchen Günter
Publication year - 2010
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.200903465
Subject(s) - allylic rearrangement , phosphoramidite , iridium , chemistry , catalysis , olefin fiber , photochemistry , combinatorial chemistry , medicinal chemistry , stereochemistry , organic chemistry , dna , biochemistry , oligonucleotide
Mechanistic aspects of allylic substitutions with iridium catalysts derived from phosphoramidites by cyclometalation were investigated. The determination of resting states by 31 P NMR spectroscopy led to the conclusion that the cyclometalation process is reversible. A novel, one‐pot procedure for the preparation of (π‐ allyl)Ir complexes was developed, and these complexes were characterised by X‐ray crystal structure analyses and spectral data. They are fully active catalysts of the allylic substitution reaction. DFT calculations on the allyl complexes, transition states of the allylic substitution and product olefin complexes gave further mechanistic insight.