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The para‐Claisen rearrangement of aryl 1‐propargyl ethers involves two‐step [3,3]‐sigmatropic rearrangements and dearomatization process, which has high activation barriers and is of challenge. Here we discovered thermal para‐Claisen rearrangement of naphthyl 1‐propargyl ethers, and it enabled the formation of formal para‐C−H propargylation products upon rearomatization. Chirality transfer occurred...
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