Treatment of RCH2CCCOX with [60]fullerene in the presence of tricyclohexylphosphine (PCy3) afforded a [2 + 2] cycloaddition product (1: R = H, X = OMe); 2: R = Bu, X = OMe; 3: R = X = Me which resulted from addition of the β, γ-carbons of RCH2CCCOX to the carbon-carbon double bond across a 6/6 ring junction of [60]fullerene.