A photocatalyzed formal (3+2) cycloaddition has been developed to construct original polysubstituted -SCF3 cyclopentanones in a regio-and diastereoselective manner. This building block approach leverages trifluoromethylthio alkynes and branched / linear aldehydes, as readily available reaction partners, in consecutive hydrogen atom transfers and C-C bond formations.

Difluoromethylthio alkynes are also compatible subtrates.

Furthermore, the potential for telescoped reaction starting from alcohols instead of aldehydes was demonstrated, as well as process automatization and scale-up under continuous microflow conditions. This prompted density functional theory (DFT) calculations to support a radical-mediated cascade process.