The partial zipping of a fullerene orifice was achieved by a water-mediated thermal rearrangement at 150 °C for one day while the orifice size changed from 16- to 14-membered ring with the generation of a fused pentagon. The addition of B(C6 F5 )3 was found to facilitate the reaction likely due to the coordination to carbonyl groups on the orifice. By extending the reaction time, the decarbonylation took place to give another 14-membered-ring orifice where the Michael addition of water occurred under acidic conditions. The computational study suggested that the formation of a carboxylic acid and Fischer-type carbene plays a key role in the C-C bond cleavage/reformation processes during the rearrangement.
Keywords: C−C bond cleavage; decarbonylation; fullerenes; rearrangement; ring contraction.
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