A facile and convenient protocol for the regioselective construction of functionalized 2-hydroxybenzophenones is described. This protocol involves the Sc(OTf)3/BF3·OEt2-catalyzed benzannulation of 2-vinyloxirans with 3-formylchromone, which involves cascade in situ diene formation, [4 + 2] cycloaddition, elimination, and ring-opening strategies. Moreover, it provides an expedited synthetic pathway to access biologically intriguing 1,4-naphthoquinones and anthraquinones including vitamin K3 and tectoquinone. The synthesized compounds also hold potential for use as UV filters and show promise as chemosensors for Cu2+ and Mg2+ ions.