A complementary copper-catalyzed and electrochemical aminosulfonylation of O-homoallyl benzimidates and N-alkenyl amidines with sodium sulfinates was developed. The terminal alkene substrate produced sulfone-containing 1,3-oxazines and tetrahydropyrimidines in the presence of Cu(OAc)2, Ag2CO3, and DPP, and under similar reaction conditions, sulfonylated tetrahydro-1,3-oxazepines were prepared from 1-aryl-substituted O-homoallyl benzimidates in moderate to good yields. For certain electron-rich 1,1-diaryl-substituted alkene substrates, the corresponding tetrahydro-1,3-oxazepines could also be obtained in similar or even higher yields via a green electrochemical technique.