Divergent Synthesis of Homoallylic and Allenic Sulfides, Selenides, and S,C-Sulfonium Ylides by Ruthenium Catalysis

Compounds bearing benzothiophene and thioether motifs have attracted broad interest because of their prevalence across natural products, advanced materials, agrochemicals, and therapeutic agents. Importantly, many marketed drugs incorporate C-S linkages, underscoring the ongoing need for streamlined methods to construct sulfur-containing molecules. We herein report ruthenium-catalyzed divergent synthesis of homoallylic and allenic sulfides, selenides, and S,C-sulfonium ylides from iodonium ylides. This work features a ruthenium-catalyzed Doyle-Kirmse-type reaction of iodonium ylides, followed by a rare decarbonylation to deliver homoallylic and allenic sulfides/selenides. The method operates under mild conditions with broad substrate scope and good functional group tolerance, while extending the Doyle-Kirmse reaction beyond diazo compounds by employing stable, nonexplosive iodonium ylides. Furthermore, we also describe a ruthenium-catalyzed transylidation strategy that couples <i>N</i>-acyl sulfenamides with iodonium ylides to generate a wide range of S,C-sulfonium ylides under mild conditions. This method features a broad substrate scope, good tolerance toward functional groups, and an inexpensive ruthenium catalyst. Moreover, scale-up and subsequent derivatization experiments demonstrate its practicality. Overall, this protocol provides a versatile entry to diverse sulfonium ylides and opens opportunities for their application in synthetic chemistry.