Ir-catalysed allylic substitution: mechanistic aspects and asymmetric synthesis with phosphorus amidites as ligands

Ir-catalysed allylic alkylations of enantiomerically enriched monosubstitut ed allylic acetates proceed with up to 79% retention of configuration using P(OPh)(3) as ligand; further evidence supports the assumption of sigma-all yl complexes as intermediates, and high regio- and enantioselectivity in as ymmetric allylic alkylations of achiral or racemic substrates is achieved w ith phosphorus amidites as ligands.