“Truncated” Pagodanes — Synthesis of Functionalized [1.1.1.1] and [1.1.1.0] Pagodanes

“Truncated” 1.1.1.1] pagodanes like the 1.1.0.0] and 0.0.0.0] homologues3 and 4 (E_Str = 146.1 – 171.5 kcal mol^?1, MM2) are potential precursors of unusual unsaturated homoconjugated radical cations and σ-bishomoaromatic dications. Attempts are presented toward the synthesis of 3 - starting out from 1.1.1.1] pagodane-4,9-dione 9 and diaza 2.2.1.1] pagodadiene 11 by cycloelimination (unsuccessful) and by Favorskii-type ring contraction methodologies. Control experiments with the model diketone 19 documented the limitations for α,α′-difunctionalization of 9 as the prerequisite for one-pot double Favorskii-type ring contraction. A de novo synthesis for such α,α′-disubstituted derivatives of 9(54) was not sufficiently expeditious to open a practical access to 3. Sequential double bridgehead hydroxylation of 9, successfully practized with model 19, similarly suffered from inherent cage effects and allowed only limited yields of 1.1.1.0] pagodanone 10, the intermediate on the way to 3.