Herein we report a dearomative syn-1,4diamination protocol using simple nonactivated arenes and amines. This one-pot method utilizes arene arenophile para-cycloadducts, formed via visible-light mediated [4+2]-photocycloaddition that undergoes formal allylic substitution with amine nucleophiles under Pd catalysis. The products are obtained with exclusive syn-1,4-selectivity; the method permits enantioselective desymmetrization of naphthalene, as well as elaborations of amine-containing drug molecules. Furthermore, the resulting unsaturated products are amenable to numerous options for diversification. Overall, this novel dearomative functionalization strategy offers rapid and straightforward access to complex building blocks, which are difficult to prepare otherwise, from simple arenes.