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Updated: Jul 19, 2026

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[2,3] Sigmatropic Rearrangement of Allylic S-Acylsulfonium Ylide Intermediates Generated from Rhodium-Catalyzed
Chad Cribbs1, Jason R Combs1, Viktor Gevirtzman1
1Department of Chemistry, University of California, Irvine, California 92617-2025, United States.
Abstract:
Allyl thioesters, thiocarbonates, thiocarbamates, and thiocyanates are shown to undergo rhodium-catalyzed addition of carbene groups, generated from diazo compounds, to afford S-acyl sulfonium ylides that undergo [2,3] sigmatropic rearrangement. Competing side reactions such as cyclopropanation and [1,2] acyl shifts are not observed. The reaction works with a variety of sulfur functional groups, including thioesters, thiocarbonates, thiocarbamates, and thiocyanates, affording densely functionalized products. The reaction works well with trimethylsilyldiazomethane (TMSD) and α-aryl diazoesters.
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