In this paper, we report the results of our investigations into the development of a method for the general reaction of unbiased silyl enol ethers (1) with a wide variety of heteronucleophiles, including carboxylic acids, thiols, alcohols, amines, azides, and even CO2 for the first time. Conveniently, in all instances, the same I(III) reagent is used. Thus the synthesis of substrate-specific iodanes is avoided, which contributes to the generality and applicability of the method. The mechanism of the reaction has been studied experimentally and by DFT calculations, and an unusual enolonium intermediate with a halogen-bonded bromide atom is proposed. From this enolonium, an a-brominated carbonyl intermediate is formed, which is key for the high efficiency and the broad scope of the umpolung reaction.