We have developed an umpolung method for the cross-nucleophile coupling of enol derivatives with a variety of nucleophiles, using a single iodine(III) reagent. The reactions occur with good efficiency, and by-products are not formed. Using the method described here, CO2 has been used, in the form of anionic carbamates, in their reaction with silyl enol ethers for the first time. Additionally, benzoic acids, alcohols, thiols, primary and secondary amines, malonate and an azide have been used as nucleophiles in the transformation. We have also used this approach to derivatize natural products and drugs. Mechanistic evidence and DFT calculations have shown that abromoketones are formed as reaction intermediates. DFT calculations indicate that the mechanism may proceed via enolonium species containing I-Br halogen bonds. This may be key for the generality and high selectivity of the reaction.