A method providing expeditious access to chiral allylic amines via a Rh(I)/bicyclo[2.2.1]heptadiene-catalyzed enantioselective alkenylation of N-tosyl aldimines with potassium alkenyltrifluoroborates under microwave irradiation is described. The rate of the asymmetric 1,2-addition reaction, conducted in the presence of 1 mol % of the catalyst, was significantly enhanced as compared to when the standard heating method was applied while still providing the corresponding products without decrease in enantioselectivity.