[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.

We disclose in this study a Ni 6 AlO x catalyst prepared by coprecipitation for the reductive amination of biomass-derived aldehydes and ketones in aqueous ammonia under mild reaction conditions. The catalyst exhibited 99% yield toward 5-aminomethyl-2-furylmethanol in the reaction of 5-hydroxymethyl furfural with ammonia at 100 °C for 6 h under 1 bar H 2 . The catalyst was further extended to the reductive amination of a library of aromatic and aliphatic aldehydes and ketones with a yield in the range 81–90% at optimized reaction conditions. Besides, 5-hydroxymethylfurfural could react with a library of primary and secondary amines with yields in the range 76–88%. The catalyst could be easily recycled and reused without apparent loss of activity in four consecutive runs.

This review covers the hydroamination of non-activated alkenes with simple amines, with a special focus on ammonia.