Concise Access to Naphthalene Building Blocks for Naphthylisoquinoline Alkaloid Synthesis via Transition‐Metal Catalysis

A refined and therefore more (cost)efficient synthetic pathway towards 3‐functionalized and orthogonally diprotected 5‐bromo‐1,8‐dioxynaphthalenes is reported. The latter has been very recently employed as highly suitable building blocks for the total synthesis of 5‐(naphtha‐8‐yl)isoquinoline alkaloids. Relying on the application of different transition‐metal catalyzed reactions, namely C−H oxidation, Hartwig borylation and C,C cross‐coupling reactions the desired precursors for future atroposelective synthesis of 5,8’‐naphthylisoquinoline alkaloids and derivatives became accessible in a concise fashion.