TfOH/HFIP Cluster-Promoted Divergent C–C Bond Cleavage and Reconstruction of Alkynoic Acids

C–C bond cleavage and reconstruction of carboxylic acids is predominantly directed at the C–C(O) position. Herein, we have successfully developed a TfOH/HFIP cluster-promoted divergent strategy for the C–C bond cleavage of alkynoic acids and their subsequent reconstruction with arenes, affording selective access to distinct molecular architectures through tunable decarboxylation or deketonation. This platform not only facilitates mild decarboxylative functionalization but also establishes an unprecedented deketonative functionalization pathway for carboxylic acids.