Ir-catalysed asymmetric allylic substitutions with cyclometalated (phosphoramidite)Ir complexes--resting states, catalytically active (pi-allyl)Ir complexes and computational exploration.

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 (pi- allyl)Ir complexes was developed, and these complexes were characterised by X-ray crystal structure analyses and spectral data.

Synthesis of alpha,beta-unsaturated gamma-lactams via asymmetric iridium-catalysed allylic substitution.

Syntheses of alpha,beta-unsaturated gamma-lactams are described that are based on ring-closing metathesis in combination with enantioselective Ir-catalysed allylic amination using N-Boc-N-(but-2-enoyl)-amine as a pronucleophile. As an example application, the synthesis of a Baclofen analogue is presented.