Synthesis of 4‐Acylchromene via Highly Chemoselective Iodine‐Catalyzed Cyclization of Alkynylarylether Dimethylacetals

4‐Acylchromene is an important core structure found in bioactive natural products and bioactive synthetic compounds. Moreover, this core structure is frequently used as a key precursor for the synthesis of more complex molecules. In this work, we discovered that a combination of acetone and catalytic I 2 could lead to selective activation of acetal in alkynylarylether dimethylacetal substrates while alkyne moiety remained intact. This activation of acetal led to the generation of oxonium ion intermediate which triggered intramolecular cyclization and elimination of methanol to provide the desired 4‐acylchromene as the sole product in up to 95% yield. Moreover, this method could be applied in a broad range of substrates under a mild and metal‐free catalytic conditions for the synthesis of 4‐acylchromene derivatives.