Beschreibung:
<jats:title>Abstract</jats:title><jats:p>In this account, we describe our journey leading to the discovery of a generally applicable umpolung method for the α-functionalization of ketones. Central to this reaction is the cyclic hypervalent fluoro-iodane, which is mostly known for various alkene functionalizations enabling, for example, the synthesis of fluoro-benzoxazepines, indoles, and ketones. During this work, we encountered α-functionalized ketones as minor side products. This observation prompted us to further investigate this reactivity, thus revealing a directed umpolung of pyridyl ketones by the fluoro-iodane. The key to the success was the unexpected non-covalent interaction between the nucleophile, substrate, and iodane.</jats:p><jats:p>1 Introduction</jats:p><jats:p>2 Cyclizations Triggered by the Fluorination of Styrenes</jats:p><jats:p>3 Umpolung Reactions Facilitated by Hypervalent Iodanes</jats:p><jats:p>4 Discovering and Evolving a Fluoro-Iodane-Triggered Regioselective α-Functionalization of Carbonyl Compounds</jats:p><jats:p>5 First Investigations on the Nitrogen-Directed Umpolung</jats:p><jats:p>6 Conclusion</jats:p>