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Mechanistic studies of the reaction between 3‐arylprop‐2‐ynyl esters and aldehydes catalyzed by BF3⋅Et2O were performed by isotopic labeling experiments and quantum chemical calculations. The reactions are shown to proceed by either a classical alkyne–carbonyl metathesis route or an unprecedented addition–rearrangement cascade. Depending on the structure of the starting materials and the reaction...
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