Subsequent diazo transfer reaction led to the corresponding diazo compound 13. The following intramolecular Buchner reaction, vital for our outside → inside strategy, required excessive catalyst optimization: After investigation of a variety of Rh(II) and Cu(II) complexes, we identified Cu(hFacac)2 as suitable catalyst for the desired Buchner dearomatization to give triasterane 14 (for optimization see Supporting Information). Remarkably, only few of the catalysts employed gave the desired product 14 at all, whereas the Buchner reaction catalyzed by Cu(hFacac)2 did not show any traces of otherwise competing C-H-insertions. Finally, dehydrogenative oxidation using DDQ gave homoannulene ester 15. To support the connectivity and stereochemistry of the desired products, crystal structures were obtained for 11, 12b-14b and 15 . Gratifyingly, this allowed for analysis of bond lengths with foresight to potential homoaromaticity (see below).