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 N-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.