Primary and unbranched secondary amines are obtained by the highly selective hydroaminomethylation of olefins with ammonia [Eq. (a)]. The selectivity is readily controlled with a new dual Rh/Ir catalyst in a two-phase system.

A concept for the homogeneous hydroformylation of internal olefins to linear aldehydes is presented. The internal olefin is isomerized to its terminal isomer by one catalyst prior to hydroformylation by a second transition metal catalyst. The terminal olefins obtained by isomerization react preferentially to give linear aldehydes. The viability of the concept is demonstrated by a dual catalytic Ru/Rh system with chelating phosphanophosphite ligands. Thus, the isomerization ± hydroformylation sequence represents a promising starting point for the economically important refinement of internal olefins.

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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