Iodonium(III) Ylide: An Iodoalkylation Reagent with Aryne

A tandem Hexadehydro-Diels–Alder (HDDA)/[2 + 2] cycloaddition/aryl migration reaction of iodonium ylide with tetrayne is described, in which iodonium ylide served as a unique double bond and reacted with aryne to form a four-membered iodonium(III) cycle, then converted to iodoarene after aryl group migration from iodine to adjacent carbon. This strategy allows the efficient construction of fully substituted iodoarene compounds.