Sensitive functional groups are tolerated in an iodine–zinc exchange reaction catalyzed by Li(acac). Aryl and heteroaryl diorganozinc compounds with keto, aldehyde, or isothiocyanate substituents can be prepared by this method (see example in scheme; acac=acetylacetone, NMP=1‐methyl‐2‐pyrrolidinone). Such zinc reagents serve as substrates for a wide variety of coupling reactions.