Silver‐Mediated Cascade Synthesis of Open‐Cage Fullerenes from C₆₀ and Propargylic Carbonates

In recent years, open‐cage fullerenes (i.e., fullerene derivatives featuring an orifice within their cage structure) have attracted significant attention across multiple research areas in materials, coordination, supramolecular, and biomolecular chemistry. However, the methodology available for the preparation of open‐cage fullerenes remains limited. Herein, it is discovered that upon heating fullerene C 60 with propargylic carbonates in the presence of silver trifluoroacetate, a cascade of reaction steps is initiated, resulting in the one‐step synthesis of the corresponding open‐cage bisfulleroids. Moreover, the feasibility of introducing various substituents via this methodology is confirmed. Notably, the proposed protocol facilitates the synthesis of bisfulleroid derivatives, wherein a hydrogen atom resides on one side of the bridgehead carbon at the orifice, while an aryl or alkyl substituent is strategically introduced on the opposite side. This approach provides structural diversity for the synthesis of open‐cage fullerenes and is expected to promote the widespread application of open‐cage fullerene derivatives.