Iridium-catalysed allylic substitution: Stereochemical aspects and isolation of Ir-III complexes related to the catalytic cycle

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 regioand enantioselectivity of up to 86% ee in asymmetric allylic alkylations of achiral or racemic substrates is achieved...

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Bibliographic Details
Published inEuropean journal of inorganic chemistry no. 10; pp. 2569 - 2586
Main Authors Bartels, B, Garcia-Yebra, C, Rominger, F, Helmchen, G
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 01.10.2002
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Physical Sciences
Science & Technology
ASYMMETRIC-SYNTHESIS
CARBON
HYDROGEN-BOND
ALKYLATION
asymmetric catalysis
allyl complexes
STEREOSELECTIVE FORMATION
iridium
ALCOHOLS
AMINATION
OXIDATIVE-ADDITION
BOND ACTIVATION
allylic substitution
NMR spectroscopy
SELECTIVE STABILIZATION
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Summary: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 regioand 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-tos-ylbenzylamide 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 (pi-allyl)Ir-III complexes were characterised by X-ray crystal structure analysis and spectroscopic data.
ISSN:1434-1948
1099-0682