Rh-Catalyzed [2,3]-Sigmatropic Rearrangement of Alkynyl Carbenes with Allyl Sulfides to Access Sulfide-Substituted 1,5-Enynes

This study describes the development of Rh-catalyzed[2,3]-sigmatropicrearrangement of alkynyl carbenes with allyl sulfides. The protocolexhibits equitable functional group tolerance and allows the formationof a variety of synthetically valuable sulfide-substituted 1,5-enyneproducts. To the best of our knowledge, this is the first exampleof [2,3]-sigmatropic rearrangement of alkynyl carbenes. DFT analysissupports the involvement of rhodium carbene generation, sulfoniumylides formation, and [2,3]-sigmatropic rearrangement pathway.

Automated summary

This study presents the development of the Rh-catalyzed[2,3]-sigmatropic rearrangement of alkynyl carbenes with allyl sulfides. The protocol shows good tolerance towards various functional groups and enables the synthesis of valuable sulfide-substituted 1,5-enyne products. It is the first example of [2,3]-sigmatropic rearrangement of alkynyl carbenes. DFT analysis confirms the involvement of rhodium carbene generation, sulfoniumylides formation, and [2,3]-sigmatropic rearrangement pathway.