The Mechanistic Perspective of IV Iodoxolones

The historical development of ortho‐iodoxybenzoic acid (IBX) and the Dess‐Martin periodinane (DMP) is précised to introduce a comprehensive catalogue of the plausible reaction mechanisms that have been proposed to explain their organic chemistry. Each example sourced from the IV iodoxolone mechanistic literature is concisely discussed with reference to relevant structures, presented in the format of a chemical reaction diagram. Where apt, electron pushing arrow annotations systematically inspect electron redistributions typically associated with proton migration assisted bond formation or rupture. Along the journey, reviewing the many facetted repertoire of oxidations that can be accessed by an IV iodoxolone reagent, provides critical insight into the versatility and applications of the mild oxidant(s), the underlying organic chemistry, as well as acknowledgement for the scientists who have unpacked the cornucopia of IV iodoxolone chemistry. A narrative is extolled of a how following the intrinsic reaction coordinate (IRC) using density functional theory (DFT) elucidated the general mechanism of IBX mediated primary (1°) alcohol or 1° amine oxidation, which had previously been the subject of a robust interdisciplinary debate within the chemistry community, as to whether proton abstraction or isomerisation represents the rate determining step.