Synthesis, Characterization and Unusual Reactivity of Vinylbenziodoxolones—Novel Hypervalent Iodine Reagents

Abstract

A novel type of hypervalent iodine(III) reagents, vinylbenziodoxolones (VBX), has been synthesized in a one-pot reaction from 2-iodobenzoic acid. VBX is bench stable, has been thoroughly characterized and the cyclic structure is supported by X-ray analysis. The reactivity of VBX was investigated in vinylation of nitrocyclohexane, and delivered vinylated products with opposite regioselectivity compared to acyclic vinyl(aryl)iodonium salts. The reagents could become a powerful tool in vinylation reactions under both metal-free and metal-catalyzed conditions.

Photoredox Imino Functionalizations of Olefins

“…Furthermore,b yu sing hypervalent IBX reagents, [23] we have developed unprecedented radical imino cyanation (5l), olefination (5m), and alkynylation (5n)p rocesses.T he successful formation of 5l is interesting, as recent literature reports described the cyanating reagent to be able to react with only C(sp 3 )-radicals a to ah eteroatom. [12i] Ther eagent used for the formation of 5m [24] has not been used before in radical manifolds,and makes this example the first use of IBX reagents as vinylation partners in free-radical processes.…”

“…The successful formation of 5 l is interesting, as recent literature reports described the cyanating reagent to be able to react with only C(sp 3 )‐radicals α to a heteroatom 12i. The reagent used for the formation of 5 m 24 has not been used before in radical manifolds, and makes this example the first use of IBX reagents as vinylation partners in free‐radical processes.…”

Photoredox Imino Functionalizations of Olefins

“…The successful formation of 5 l is interesting, as recent literature reports described the cyanating reagent to be able to react with only C(sp 3 )‐radicals α to a heteroatom . The reagent used for the formation of 5 m has not been used before in radical manifolds, and makes this example the first use of IBX reagents as vinylation partners in free‐radical processes.…”

C‐Terminal Bioconjugation of Peptides through Photoredox Catalyzed Decarboxylative Alkynylation

“…Them ethodology was applied to vinyl-benziodoxolone (VBX) reagent 7 [25] to afford 8 in 82 %y ield as the E isomer.T he use of alkyl or silyl substituted EBXs led to only very low yields. Electron-withdrawing groups were tolerated in para position on the benzene,including CF 3 ,bromine,aldehyde,or cyanide (6b-e).…”