Enantioselective synthesis of (+)(R)- and (-)(S)-nicotine based on Ir-catalysed allylic amination.

The synthesis of nicotine with enantiomeric excess of >99% ee was accomplished by asymmetric Ir-catalysed allylic amination followed by ring closing metathesis and racemization-free double bond reduction.

Carbocycles via enantioselective inter- and intramolecular iridium-catalysed allylic alkylations.

Carbocycles with > 90% ee were prepared via Ir-catalysed asymmetric allylic alkylation/ring closing metathesis sequences or enantioselective Ir-catalysed intramolecular allylic alkylations.

Highly enantioselective syntheses of heterocycles via intramolecular Ir-catalyzed allylic amination and etherification.

[reaction: see text] Enantioselective Ir-catalyzed intramolecular allylic aminations and etherifications are described. Up to 97% ee was achieved using catalysts prepared by in situ activation of mixtures of phosphorus amidites and [Ir(COD)Cl]2. Sequential aminations of bis-allylic carbonates, involving an inter- followed by an intramolecular reaction, gave trans-N-benzyl-2,5-divinylpyrrolidine and trans-N-benzyl-2,6-divinylpiperidine with > or = 99% ee. New phosphorus amidites as well as improved conditions for intermolecular aminations are reported.

First intramolecular enantioselective iridium-catalysed allylic aminations.

Enantioselective iridium-catalysed intramolecular allylic aminations, using phosphinooxazolines or phosphorus amidites as ligands, provided ee values of >90%, at a catalyst loading of <0.5 mol-%, and displayed a marked preference for intra- over corresponding intermolecular reactions.