An unexpected cascade reaction of 2-aminobenzaldehydes with arylamines catalyzed by scandium pentafluorobenzoate [Sc(Pfb)3] was reported as a facile strategy for the efficient synthesis of a novel class of polycyclic ring-fused aminals N-substituted-6,7,11b,13-tetrahydro-6,12-[1,2]benzenoquinazolino[3,4-a]quinazolin-13-amines 1. Under similar conditions, a series of the analogues of Tröger's base, 13-substituted-5,6,11,12-tetrahydro-6,12-epiminodibenzo[b,f][1,5]diazocines 2 were obtained when the arylamines were replaced by methanamines. A possible mechanism for the formation of 1 and 2 was proposed.