Sulfinate salts have attracted considerable attentions due to their versatile reactivity. They have emerged as highly useful building blocks for the construction of all kinds of sulfonyl‐group containing molecules, such as sulfones or sulfonamides, and for the construction of various carbon–carbon‐ and carbon–heteroatom‐bonds via sulfur dioxide (SO2) extrusion. Herein, we want to summarize the latest developments in the synthesis of sulfinate salts. Both improvement of classical methods and the development of various novel protocols will be discussed. Also selected one‐pot methods directly utilizing in situ generated sulfinate salts as intermediates will be covered in this review article.

Molecules containing a sulfonyl functionality, such as sulfones, sulfonyl chlorides or sulfonamides play an important role in organic chemistry and have found widespread application, especially in the construction of biologically active compounds. Recently, methods for the synthesis of the sulfonyl moiety utilizing sulfur dioxide as a key building block have received considerable attention. In this context, radical-based transformations with sulfur dioxide have emerged as a new and attractive approach for the construction of the sulfonyl functional group. This short review highlights recent advances in the use of sulfur dioxide in radical reactions and covers the historical background, which forms the basis for these current progresses. Limitations of the existing methods and potential further developments will be discussed.

Organic photo- and electrochemistry currently experience tremendous attention in organic synthesis as both techniques enable reagent-less activation of organic molecules without using expensive and hazardeous redox reagents. The incorporation of...

An efficient cross-coupling of sodium or lithium sulfinates with aryl iodides, using a combination of nickel and photoredox catalysis, is described. The dual catalyst system enables a versatile synthesis of aryl sulfones at room temperature in good yields and displays a broad functional group compatibility. The potential utility of this method in the late-stage diversification of complex molecules and in the conversion of organolithium reagents and sulfur dioxide into sulfones is demonstrated.

Sulfones play a pivotal role in modern organic chemistry. They are highly versatile building blocks and find various applications as drugs, agrochemicals, or functional materials. Therefore, sustainable access to this class of molecules is of great interest. Herein, the goal was to provide a summary on recent develop-ments in the field of sustainable sulfone synthesis. Advances and existing limitations in traditional approaches towards sulfones were reviewed on selected examples. Furthermore, novel emerging technologies for a more sustainable sulfone synthesis and future directions were discussed.