The reactivity of the double-stranded hydrocarbon cycle with two ether bridges (
1) toward iodotrimethylsilane (TMSI) was investigated in some detail. The carbon skeleton of cycle
1 resembles the belt regionof a C
84 fullerene which makes it a potential precursor to the long sought after fully aromatic derivative.Upon exposure to TMSI, cycle
1 undergoes a cascade of reactions which involve different states ofiodination/reduction which ultimately lead to the hydrogenated cycle
5a, whose structure was proven bysingle-crystal X-ray analysis. A deeper insight into mechanistic aspects of this sequence of conversionswas gained by performing the reaction under dry and wet conditions, whereby the latter involved bothnormal and deuterated water. With the help of detailed NMR correlation studies and DFT computations,all important aspects were clarified including an unexpected selective H/D exchange at the naphthalenicmoieties.
