Structurally Constrained Cyclic (Diacyloxyiodo)Arenes as an Enabling Platform for Hypervalent Iodine(III) Chemistry

Hypervalent iodine(III) chemistry has unlocked remarkable potential in synthetic and catalytic applications over the past decades, yet its development has been constrained by biased thermodynamics between iodine(I) and iodine(III) species, relying on unstable or environmentally unfriendly oxidants and complex electrocatalytic platforms. Here, structurally constrained cyclic (diacyloxyiodo)arenes are presented as a transformative platform to resolve the reactivity/selectivity-generality paradox, enabling one-pot synthesis of diverse hypervalent iodine(III) reagents. The synthetic utility and sustainability of the in situ controlled-release approach are demonstrated through catalytic reactions, asymmetric variations, and biocompatibility studies, including peptide modifications. Central to this success is the discovery of cyclic (diacyloxyiodo)arenes-a previously unexplored chemical entity. DFT calculations reveal that spatial dianion control via intramolecular secondary bonding enhances reactivity and selectivity while delivering superior outcomes.