1,2‐Sulfonylative‐Arylation of Acrylamides via Strain‐Release‐/Aromaticity‐Driven Radical Generation and SO 2 ‐Capture under Photoredox Catalysis to Access S(VI)‐Oxindoles

γ‐Keto sulfones, despite being a medicinally relevant building block, have never been integrated with the bioactive oxindole scaffold present in several alkaloid natural products. On the other hand, strategies involving SO 2 capture in organic molecules to access value‐added products are gaining momentum. Therefore, a strategy en route to γ‐keto alkylsulfonylated oxindoles bearing a β ‐all‐carbon quaternary center is disclosed. Toward this goal, the bisfunctionalization of N‐(hetero)arylacrylamides has been realized via the strain‐release driven ring‐scission of strained 3°‐cyclopropanols in the presence of DABSO under visible‐light photoredox catalysis to access a library of γ‐keto alkylsulfonylated oxindoles. Also, the aromaticity‐driven bond‐scission in pro‐aromatics like 4‐alkyl‐1,4‐DHPs in the presence of Na 2 S 2 O 5 under visible‐light photoredox catalysis has been exploited to trigger the alkylsulfonylative‐arylation of N‐(hetero)arylacrylamides to access a library of alkylsulfonylated oxindoles featuring a β‐all‐carbon quaternary center. Broad substrate scope is demonstrated, and the mechanistic probing studies have been complemented with DFT calculations. Also, moderate to potent cytotoxic activity is observed against the tested triple‐negative breast cancer cell lines for some of the synthesized sulfonylated oxindole derivatives. Further, evaluation of the mechanism of cell death for the most potent oxindole analog revealed that it induces apoptosis in a concentration‐dependent manner.