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Iridium‐Catalysed Allylic Substitution: Stereochemical Aspects and Isolation of Ir III Complexes Related to the Catalytic Cycle
Author(s) -
Bartels Björn,
GarcíaYebra Cristina,
Rominger Frank,
Helmchen Günter
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200210)2002:10<2569::aid-ejic2569>3.0.co;2-5
Subject(s) - chemistry , allylic rearrangement , iridium , nucleophile , medicinal chemistry , substitution reaction , enantioselective synthesis , ligand (biochemistry) , lithium (medication) , catalysis , denticity , stereochemistry , crystal structure , organic chemistry , medicine , biochemistry , receptor , endocrinology
Ir‐catalysed allylic alkylations of enantiomerically enriched monosubstituted allylic acetates proceed with up to 87% retention of configuration using P(OPh) 3 as ligand. High regio‐ and enantioselectivity of up to 86% ee in asymmetric allylic alkylations of achiral or racemic substrates is achieved with monodentate phosphorus amidites as ligands. Lithium N ‐tosylbenzylamide was identified as a suitable nucleophile for allylic aminations. Of particular importance is the use of lithium chloride as an additive, generally leading to increased enantioselectivities. Two (π‐allyl)Ir III complexes were characterised by X‐ray crystal structure analysis and spectroscopic data.