Highly regioselective isomerization-hydroaminomethylation of internal olefins catalyzed by Rh complex with Tetrabi-type phosphorus ligands.

A highly regioselective isomerization-hydroaminomethylation of internal olefins has been developed. A 95.3% amine selectivity and 36.2 n/i ratio were obtained for 2-octene with a Tetrabi ligand and Rh(acac)(CO)(2), and a TON of linear amine was achieved of 6837 with a 39.1 n/i ratio of amine. The m-CF(3)-Ph substituted ligand was the best of the applied Tetrabi-type phosphorus ligands for different internal olefins, as up to a 99.2% amine selectivity and 95.6 n/i ratio were obtained for 2-pentene.