Highly selective isomerization of N-allylamines catalyzed by ruthenium and rhodium complexes

Synthesis of enamines via isomerization of N-allylamines (R1R2NCH2CHCH2 and PhMeNCH2CHCHSiMe3) catalyzed by [RhH(CO)(PPh3)3] or [RuClH(CO)(PPh3)3] is described. In the case of the ruthenium complex, double bond migration was successful only for allylamines with bulky groups at the nitrogen atom. A strong E-selectivity (resulting from specific coordination effects, as demonstrated by theoretical calculations) in the isomerization of allylamines was observed.