Description:
<jats:title>Abstract</jats:title><jats:p>The reactivity of <jats:italic>ortho</jats:italic>‐functionalized <jats:italic>N</jats:italic>‐heterocycle‐substituted iodoarenes (NHIAs) as organocatalysts in iodine(I/III)‐mediated oxidations was systematically investigated in the <jats:italic>α</jats:italic>‐tosyloxylation of ketones as the model reaction. During a systematic catalyst evolution, it was found that NH‐triazoles and benzoxazoles have the most significant positive influence on the reactivity of the central iodine atom. A further catalyst improvement which focused on the substitution pattern of the arene revealed a remarkable <jats:italic>ortho</jats:italic>‐effect. By introduction of an <jats:italic>o</jats:italic>‐OMe group we were able to generate a novel NHIA with a so far unseen catalytic efficiency. This new catalyst is not only easy to synthesize but also enabled the <jats:italic>α</jats:italic>‐tosyloxylation of carbonyl compounds at the lowest reported catalyst loading of only 1 mol%. Finally, the performance of this iodine(I) catalyst was successfully demonstrated in intramolecular oxidative couplings of biphenyls and oxidative rearrangements.</jats:p><jats:p><jats:boxed-text content-type="graphic" position="anchor"><jats:graphic xmlns:xlink="http://www.w3.org/1999/xlink" mimetype="image/png" position="anchor" specific-use="enlarged-web-image" xlink:href="graphic/adsc201901356-toc-0001-m.png"><jats:alt-text>magnified image</jats:alt-text></jats:graphic></jats:boxed-text>
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