Regioselectivity-switchable reactions hold irreplaceable importance in the construction of diversified architectures. In this work, Brønsted base-catalyzed regioselectivity-switchable annulations between alkynyl α-diketones and α-cyanoketones have been achieved for the first time, delivering a series of skeletally thoroughly different dihydrofurofuran and furan derivatives. A range of novel transformations of the products can be realized. The work also demonstrates the unique features of alkynyl α-diketone chemistry, which are in sharp contrast to the current understanding of ynone-related chemistry.
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