Asymmetric Organocatalysis in Fullerenes Chemistry: Enantioselective Phosphine‐catalyzed Cycloaddition of Allenoates onto C60

Organocatalysis and fullerenes merge: The first asymmetric organocatalytic synthesis by phosphine-catalyzed [3+2] cycloaddition of allenoates onto [60]fullerene that occurs under mild conditions giving rise to enantiomerically pure carbocyclic fullerene derivatives is reported. X-ray analysis of a cyclopenteno[60]fullerene has allowed the assignment of the absolute configuration of the new stereocenter. Furthermore, the sector rule previously used to assign the chirality in [60]fullerenes has been corrected in the light of these new experimental findings.