When Cl substitution goes rogue: highly selective templated synthesis of cis-bis(dihydrofurano)fullerenes from C60Cl6

Abstract

The attempted substitution of Cl atoms in C₆₀Cl₆ with nucleophiles formed in situ from 1,3-dicarbonyl compounds and potassium carbonate led to the realization of a highly unexpected pathway that produced fullerene derivatives with dihydrofuran rings fused to the fullerene cage. The major products incorporated two dihydrofuran addends attached to the C₆₀ cage at cis-1 and cis-2 positions, while other regioisomers were not observed. Thus, the critical problem of the selective addition of two cyclic organic addends to the fullerene cage was successfully mitigated in such an extraordinary way involving C₆₀Cl₆ as a substrate. The presented findings demonstrate the potential of using halofullerenes as templated substrates in common fullerene reactions (cyclopropanation, cycloaddition, etc.) to enhance their selectivity.