A unified, ready access to the tropoloisoquinoline alkaloids imerubrine (1), grandirubrine (2), and isoimerubrine (3) is delineated and features sequential application of the intramolecular Diels-Alder reaction of an acetylene-tethered oxazole and the [4 + 3] cycloaddition of an oxyallyl. A regioselective synthesis of 1 was achieved by stereo- and regioselective oxidation of an 8-oxabicyclo[3.2.1]oct-6-en-3-one cycloadduct by means of the Moriarty method. Such a post-cycloaddition functionalization complements the synthetic utility of an ol-alkoxy-substituted oxyallyl so as to broaden the scope of the oxyallyl [4 + 3] cycloaddition reaction.