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The intermolecular formyloxylation−arylation of stilbenes occurs in the presence of diazonium salts, a photocatalyst, visible light, and DMF. The photo-Meerwein addition products are obtained in good yields up to 76%. We propose the formation of an iminium ion intermediate, which is hydrolyzed to the product.

The visible light catalyzed methylsulfoxidation of (het)aryl diazonium salts using DMSO is illustrated. This is the first example of DMSO being used as the source of the methylsulfinyl group. The procedure tolerates a wide range of functional groups on (het)aryl diazonium salts and provides aryl methyl sulfoxides in excellent yields under mild reaction conditions.

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