Increasing the Dimensionality of Modular Domino Reactions Triggered by Oxidative Cleavage: A Two-Step Protocol Towards a Variety of Stereodefined Complex Oxygen Heterocycles†

Arylcarbinol- and benzyl-tethered octalin-diols (1/1′), which differ only by the C11 substitution at the angular position, were transformed selectively into original scaffolds of high complexity through a two-step protocol. Overall, the (11S*) configuration ensures an intramolecular Friedel–Crafts-type C13–C4 bonding through a domino process triggered by oxidative cleavage, whereas the (11R*) configuration allows for a Marson-type Friedel–Crafts C13–C2 bonding through an intramolecular nucleophilic acetal opening.