Abstract: | Enolonium species/iodo(III)enolates of carbonyl compounds have been suggested to be intermediates in a wide variety of hypervalent iodine induced chemical transformations of ketones, including α‐C−O, α‐C−N, α‐C−C, and α‐carbon–halide bond formation, but they have never been characterized. We report that these elusive umpoled enolates may be made as discrete species that are stable for several minutes at −78 °C, and report the first spectroscopic identification of such species. It is shown that enolonium species are direct intermediates in C−O, C−N, C−Cl, and C−C bond forming reactions. Our results open up chemical space for designing a variety of new transformations. We showcase the ability of enolonium species to react with prenyl, crotyl, cinnamyl, and allyl silanes with absolute regioselectivity in up to 92 % yield. |