Readily available 1‐sulfonyl‐1,2,3‐triazole and benzoquinone‐derived alcohols were employed in a synthesis protocol for the formation of α‐(2‐hydroxyphenyl)‐α‐aminoketone. The cascade reaction includes the formation of rhodium carbene, O−H bond 1,3‐insertion, Claisen rearrangement as well as aromatization. Valuable benzoxazinone and 3‐aminobenzofuran were obtained after one‐step derivatization. Moreover, an estrone derivative was modified via the protocol with extraordinary efficiency.magnified image