The hydroaminomethylation of eugenol with di-n-butylamine was performed employing a bis[(1,5-ciclooctadiene)(mu-methoxy)rhodium(1)] as pre-catalyst. In the absence of phosphines, the catalyst was efficient in the process, but the regioselectivity for amines was poor. For phosphine-promoted catalyst, the chemoselectivity at the hydroformylation step improved, but the hydrogenation of enamine intermediates was hampered. The regioselectivity within the class of amines was surprisingly high (>96%) for the linear product. The addition of triflic acid (10-20 mol%) improved significantly the efficiency of HAM. Employing the 22'-bis((diphenylphosphino)methyl)-1,1'-binaphthyl as ancillary and triflic acid as a promoter, the linear product was obtained in up to 93% yield. (C) 2012 Elsevier B.V. All rights reserved.