This review is focused on the recent advances in the chemistry of sulfur dioxide fixation through a radical process. Diverse sulfonyl compounds can be obtained efficiently under mild conditions.

Recent advances in the sulfonylation of C–H bonds with the insertion of sulfur dioxide are summarized. C–H bond sulfonylation under transition metal catalysis or through a radical process has been developed. In some cases, the sulfonylation can be performed under catalyst- and additive-free conditions, or can be facilitated by visible light irradiation. The efficiency is also studied by merging the radical process and metal catalysis.

Generation of sulfonated isobenzofuran-1(3H)-ones starting from 2-vinylbenzoic acids, aryldiazonium tetrafluoroborates, and DABCO˙(SO2)2 under photocatalysis in the presence of visible light is achieved. Additionally, the method can be extended to 4-phenylpent-4-enoic acid and 5-phenylhex-5-enoic acid.

Synthesis of allylic sulfones through a photoinduced three-component reaction of aryl/alkyl halides, potassium metabisulfite, and allylic bromides under ultraviolet irradiation at room temperature is developed. Diverse allylic sulfones are generated in moderate to good yields.

C-H bond sulfonylation of anilines with the insertion of sulfur dioxide under metal-free conditions is described. 2-Sulfonylanilines are generated in moderate to good yields through a three-component reaction of anilines, DABCO·(SO), and aryldiazonium tetrafluoroborates under mild conditions. No metal catalysts or additives are needed for this transformation. This direct C-H functionalization is highly efficient, and broad functional group tolerance is observed. A radical process is believed to be involved. In the reaction process, the arylsulfonyl radical and the tertiary amine radical cation generated in situ from DABCO·(SO), and aryldiazonium tetrafluoroborate are the key intermediates. Additionally, the tertiary amine radical cation acts as the electron carrier through a single electron transfer process.