Despite recent advances in primary sulfonamide synthesis, approaches using primary amines as starting points for direct sulfonamide construction remain elusive. Now a formal SO2 insertion into the C–N...

Radical processes involving bismuth hold great potential, but innovative strategies are required to control the reactivity of bismuth intermediates. Herein, we report a direct photochemical decarboxy...

Sulfinamides, sulfonamides, and sulfonimidamides are valuable motifs in medicinal chemistry, yet methods to synthesize alkyl variants from simple, readily available feedstocks remain scarce. In this report, we detail the synthesis of these three distinct sulfur functional groups, using readily available and structurally diverse alkyl carboxylic acids as the starting materials. The method harnesses alkyl radical generation from carboxylic acids using commercial iron salts and visible light irradiation, in combination with commercial sulfinylamine reagents, to deliver alkyl sulfinamide products. The method is operationally simple and scalable, exhibits broad functional group tolerance, and is translatable to continuous-flow synthesis. Furthermore, it facilitates late-stage diversification of complex molecules, highlighting its potential utility in medicinal chemistry applications.

A new method uses metal Lewis acids as catalysts to convert sulfonyl fluorides, fluorosulfates, and sulfamoyl fluorides with silyl amines into S–N bond-containing compounds via sulfur fluoride exchange. The reaction successfully employs Ca(NTf2)2 as a catalyst to form sulfonamides, sulfamates, and sulfamides using in situ-generated or commercially available silyl amines in 35–99% yields. Other metal Lewis acids are also demonstrated to be catalysts in SuFEx, forming sulfonamides and sulfamates in yields comparable to those of Ca(NTf2)2.

Synthetic transformations that advance through excited states proceed by unconventional mechanistic pathways and deliver products not accessible using ground-state chemistry. The breadth of these synt...