Iodination of Arenes Driven by Hypervalent Iodine-Based Halogen Bonding: Compatible with Electron-Deficient Arenes.

Iodoarenes constitute an indispensable class of organic compounds with extensive applications across diverse fields. As versatile synthetic building blocks, iodoarenes are crucial to developing pharmaceuticals, agrochemicals, and functional materials. Their efficient synthesis has long attracted significant attention. Herein, we report a unique reagent system comprising the two-coordinate hypervalent iodine reagent (phenyliodonio)sulfamate (PISA) and molecular iodine (I2). By modulating solvent and reagent stoichiometry, this system enables mild electrophilic iodination of arenes with diverse electronic properties. It exhibits excellent functional group compatibility for the late-stage iodination of complex molecules, including pharmaceuticals and natural products. DFT calculations reveal that PISA acts as an effective halogen bond donor, promoting I-I bond cleavage in I2. Concurrently, intramolecular hydrogen bonding and halogen bonding interactions involving the nitrogen and oxygen atoms of the sulfamate ligand stabilize key reactive intermediates.