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A one-pot catalytic method has been developed for the stereoselective synthesis of cyclopropane-fused cyclic amidines using CuBr2/K2S2O8 as an efficient single electron transfer (SET) oxidative system. The generality of this mild method is demonstrated with a wide variety of substrates to furnish pharmaceutically important amidines containing aza-bicyclic and novel aza-tricyclic frameworks in very good yields. A chemoselective reduction of cyclic amidines to 2-/3-azabicyclo[m.n.0]alkanes and octahydroindoles has been developed using a Na