Reactivity of Hypervalent Iodine(III) Reagents Bearing Transferable N‐Based Groups

Abstract

Hypervalent iodine reagents have the ability of inverting the polarity of functional groups bound to iodine, a reactivity known as umpolung. This reactivity makes hypervalent iodine compounds highly attractive for the creation of electrophilic synthons of known nucleophiles, resulting in novel synthetic disconnections and the formation of new Nu(nucleophile)−N bond.Electrophilic sources of nitrogen‐based groups have been known for many decades and are of great synthetic importance. Traditionally, these reagents are limited to few examples. With the use of hypervalent iodine, the transfer of a wide diversity of nitrogen sources became a possibility. This review compiles the latest reported examples of hypervalent iodine reagents capable of electrophilic transfer of nitrogen‐based groups. It showcases the preparation of such reagents, their synthetic utility, and reaction mechanisms involving these group transfer reagents.

Free Radicals in the Queue: Selective Successive Addition of Azide and N-Oxyl Radicals to Alkenes

“…Hypervalent iodine compounds are widely used in difunctionalization reactions of alkenes and generation of free radicals. − In our case, the best results were achieved using PhI­(OAc) 2 as an oxidant, and target product 3aa was obtained in 54% yield (entry 1). The use of iodic acid and potassium periodate led to nonselective oxidation of the substrate without affording the target product (entries 2 and 3).…”

Redox-Tunable Ring Expansion Enabled By A Single-Component Electrophilic Nitrogen Atom Synthon

“…Hypervalent iodine has traditionally served as a platform for the transfer of protected nitrogen species, 36,37 including azide, 38,39 bis-tosylamine, 40 sulfoximine, 41 phthalimide, 42 and diarylimines. 43 A striking recent development in hypervalent iodine chemistry is the realization of stable iodine(III) reagents bearing unprotected amines (primary 44 or secondary 45 alkyl amines, and more recently ammonia 46 ) for the direct transfer of amino groups.…”