The development of new methodologies to affect non--functionalization of arenes has emerged as a globally important arena for research, which is key to both fundamental studies and applied technologies. A range of simple arene feedstocks (namely, biphenyl, -terphenyl, -terphenyl, 1,3,5-triphenylbenzene, and biphenylene) is transformed to hitherto unobtainable multi-iodoarenes via an s-block metal sodium magnesiate templated deprotonative approach. These iodoarenes have the potential to be used in a whole host of high-impact transformations, as precursors to key materials in the pharmaceutical, molecular electronic, and nanomaterials industries.
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