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Abstract The design and optimization of novel electrocatalysts requires robust structure–activity data to correlate catalyst structure with electrochemical behavior. Aryl iodides have been gaining attention as metal-free electrocatalysts but experimental data are available for only a limited set of structures. Herein we report electrochemical data for a family of 70 aryl iodides. Half-peak potentials are utilized as proxies for reduction potentials and reveal that, despite differences in electrochemical reversibility, the potential for one-electron oxidation of 4-substituted aryl iodides to the corresponding iodanyl radicals is well-correlated with standard Hammett parameters. Additional data are presented for 3- and 2-substituted aryl iodides, including structures with potentially chelating 2-substituents that are commonly encountered in hypervalent iodine reagents. Finally, potential decomposition processes relevant to the (in)stability of iodanyl radicals are presented. We anticipate that the collected data will advance the design and application of aryl iodide electrocatalysis. 

Iminoiodinanes comprise a class of hypervalent iodine reagents that is often encountered in nitrogen-group transfer (NGT) catalysis. In general, transition metal catalysts are required to effect efficient NGT to unactivated olefins because iminoiodinanes are insufficiently electrophilic to engage in direct aziridination chemistry. Here, we demonstrate that 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) activatesN-arylsulfonamide-derived iminoiodinanes for the metal-free aziridination of unactivated olefins.¹H NMR and cyclic voltammetry (CV) studies indicate that hydrogen-bonding between HFIP and the iminoiodinane generates an oxidant capable of direct NGT to unactivated olefins. Stereochemical scrambling during aziridination of 1,2-disubstituted olefins is observed and interpreted as evidence that aziridination proceeds via a carbocation intermediate that subsequently cyclizes. These results demonstrate a simple method for activating iminoiodinane reagents, provide analysis of the extent of activation achieved by H-bonding, and indicate the potential for chemical non-innocence of fluorinated alcohol solvents in NGT catalysis. 

Hypervalent iodine compounds are a widely used class of metal-free oxidants that find application in organic synthesis. Due to the homology between the reactivity of hypervalent iodine and many transition metals ¾ oxidative addition, ligand exchange, and reductive elimination can be facile for both ¾ hypervalent iodine species find application in a variety of synthetically important organic transformations. Major limitations of these reagents include the frequent need for (super)stoichiometric loading and the intrinsically poor atom economy that results from the generation of stoichiometric quantities of iodoarene byproducts. In addition, hypervalent iodine reagents are often synthesized using metal-based terminal oxidants, which compound the resulting waste stream. Recently, substantial progress has been made to address these limitations. Here, we discuss progress towards sustainable synthetic methods for the preparation of hypervalent iodine compounds and application of those methods in the context of hypervalent iodine catalysis. The discussion is organized according to the active oxygen content, and thus atom economy, of the terminal oxidant employed. Hypervalent iodine electrochemistry and the development of recyclable iodoarenes are also discussed.