Abstract

AbstractDeveloping methods that activate C−H bonds directly with high selectivity for C−C bond formation in complex organic synthesis has been a major chemistry challenge. Recently it has been shown that photoactivation of weakly polarized C−H bonds can be carried out inside a cationic water‐soluble nanocage with visible light‐mediated host‐guest charge transfer (CT) chemistry. Using this novel photoredox activation paradigm, here we demonstrate C−C bond formation to photo‐generate 1,3‐diynes at room temperature in water from terminal aromatic alkynes for the first time. The formation of cavity‐confined alkyne radical cation and the proton‐removed neutral radical species highlight the unique C−C coupling step driven by supramolecular preorganization.

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