Modular Construction of Topologically Complex Polycyclic Acetals by Tether‐Controlled Domino Reactions

Lead tetraacetate mediated oxidative cleavage of octalin-diols (1 and 1′), tethered by variously substituted arenes placed at the angular position (C11), show switchable regioselectivity effects. A highly selective set of regiochemical outcomes can be achieved, producing a range of polycyclic acetals through competing domino paths (A–E). The modular complexity inherent in the type-1 domino precursors is derived from the C11 configuration, where the course of ring-forming processes is controlled from the chirality at a remote stereocenter (C11). For methylene-tethered type-1′ precursors, the regiochemical outcome is mainly determined by controlling the reaction parameters.