Alkene Synthesis by Photo-Wolff-Kischner Reaction of Sulfur Ylides and N-Tosylhydrazones.

A visible-light-driven and room temperature photo-Wolff-Kischner reaction of sulfur ylides and N-tosylhydrazones has been developed for the first time to provide modular access to alkene synthesis. The high functional group tolerance and broad substrate scope were demonstrated by more than 60 examples. Both E- and Z-olefinic stereochemistry in the products could be controlled with excellent stereoselectivity. A series of mechanistic studies support that the reaction should proceed through a radical-carbanion crossover pathway, specifically involving addition of photo-generated sulfur ylide radical cations to N-tosylhydrazones to form carbanions and subsequent Wolff-Kischner process.

Visible-Light-Induced Photoredox-Catalyzed Selective 1,4-Difluoroalkylesterification of 1-Aryl-1,3-dienes.

A selective three-component 1,4-difluoroalkylesterification of 1-aryl-1,3-dienes enabled by dual photoredox and copper catalysis is described. This protocol uses commercially available CF2-reagents as radical precursors and carboxylic acids as oxygen-based nucleophiles, providing access to difluoroalkylated allylic esters. This protocol could be extended to intramolecular two-component 1,4-difluoroalkylesterification to access 3-substituted benzobutyrolactones. Preliminary mechanistic studies support a radical process.