An efficient iron‐catalyzed C─H bond functionalization strategy has been developed for the direct sulfonylmethylation of benzofused ketones. This three‐component reaction employs sodium sulfinates as the sulfonyl source and dimethylacetamide (DMA) as a versatile one‐carbon synthon, enabling concurrent construction of C─C and C─S bonds. The protocol demonstrates broad functional group tolerance and proceeds under oxidative conditions using FeCl 3 and K 2 S 2 O₈. A variety of α‐tetralones, 1‐indanones, and related substrates were transf...
