Highly regioselective hydroaminomethylation of terminal olefins to linear amines using Rh complexes with a Tetrabi phosphorus ligand.

A highly regioselective hydroaminomethylation of terminal olefins catalyzed by Rh complexes with 2, 2', 6, 6'-tetrakis ((diphenylphosphino)methyl)-1, 1'-biphenyl (Tetrabi) ligand has been developed. Up to 99 % amine selectivity, 168 linear/branched amine product ratio (n/i), and 97.4 % linear amine yield has been obtained at a substrate/rhodium precursor ratio (S/Rh) of 1000 with this methodology. The turnover number was achieved 6930 at 10,000 S/Rh ratio, and the n/i can reach up to >525. Several different olefins and secondary amines have been applied successfully with high chemoselectivity (99 %), yield (>98 %), and regioselectivity (>120).