Abstract
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)IrIII complexes were characterised by X-ray crystal structure analysis and spectroscopic data.
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