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 10000 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).