The rhodium catalyzed hydroaminomethylation of I-octene with morpholine has been studied using temperature-dependent solvent systems (TMS systems). High conversions of the olefin and high selectivities to the amines are obtained in TMS systems consisting of propylene carbonate, an alkane and a semi-polar mediator, although some morpholine reacts with propylene carbonate in a side reaction. With N-octylpyrrolidone as mediator the conversion of I-octene and the selectivity of the corresponding amines reached in each time 92%. After the reaction the catalyst can be easily recovered by a simple phase separation with only a negligible loss of the rhodium catalyst. (c) 2005 Elsevier B.V. All rights reserved.