Reactions of difluoro-pentafluorosulfanyl-iodomethane (SF5CF2I) with electronically different types of alkenes

•Difluoro-pentafluorosulfanyl-iodomethane (SF5CF2I) reacted differently in Et3B-mediated radical addition reactions with electronically different alkenes.•With butyl vinyl ether the SF5CF2-substituted acetaldehyde dibutyl acetal was formed.•Less electron-rich alkenes such as dec‑1-ene, allyl acetate, and vinyl acetate provided the expected 1,2-addition products.•The strained dienes (Z,Z)-cycloocta-1,5-diene and norbornadiene gave no 1,2-addition products but led to polycyclic products oving to transannular π-cyclization of the intermediate radicals.•α,β-Unsaturated ketones did not react with SF5CF2I, while substituted benzenes reacted non-selectively and did not give any SF5CF2-containing products.