This study demonstrates an unprecedented reactivity of 2-substituted-1,4-naphthoquinones. By applying the principle of vinylogy, they have been employed as vinylogous pronucleophiles in the organocatalytic cascade reaction for the first time. This novel catalytic activation of 1,4-naphthoquinones enables access to carboannulated naphthalen-1(4 H)-one derivatives of biological importance. The site-selectivity and stereoselectivity of a process proved possible to control by the proper choice of reaction conditions.