ChemInform Abstract: The First Efficient Hydroaminomethylation with Ammonia: With Dual Metal Catalysts and Two‐Phase Catalysis to Primary Amines.

Abstract

1999amines amines (acyclic compounds) P 0060 -074The First Efficient Hydroaminomethylation with Ammonia: With Dual Metal Catalysts and Two-Phase Catalysis to Primary Amines.-The hydroaminomethylation reaction of terminal alkenes (I) and (V) with CO-NH 3 -H 2 proceeds smoothly in the presence of a dual metal catalyst Rh 2 (cod) 2 Cl 2 -Ir 2 (cod) 2 Cl 2 -phosphine ligand to furnish a mixture of primary and secondary amines. In the presence of excess ammonia, the formation of primary amines is preferred (75 to 90% selectivity as compared to secondary amines), while with decreasing amount of ammonia the formation of secondary amines (containing n-alkyl and/or iso-alkyl chains) becomes predominant due to competition between ammonia and primary amines in the reaction. The selectivity to primary amines also increases with increasing alkene chain length due to their higher solubility in the organic phase and thus improved extraction from the aqueous catalyst solution. An excellent regioselectivity [(III):(IV) = 99:1] for hydroaminomethylation is observed in the presence of the