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Hypervalent iodine (HVI) reagents have gained much attention as versatile oxidants because of their low toxicity, mild reactivity, easy handling, and availability. Despite their unique reactivity and other advantageous properties, stoichiometric HVI reagents are associated with the disadvantage of generating non-recyclable iodoarenes as waste/co-products. To overcome these drawbacks, the syntheses and utilization of various recyclable hypervalent iodine reagents have been established in recent years. This review summarizes the development of various recyclable non-polymeric, polymer-supported, ionic-liquid-supported, and metal–organic framework (MOF)-hybridized HVI reagents.1 Introduction2 Polymer-Supported Hypervalent Iodine Reagents2.1 Polymer-Supported Hypervalent Iodine(III) Reagents2.2 Polymer-Supported Hypervalent Iodine(V) Reagents3 Non-Polymeric Recyclable Hypervalent Iodine Reagents3.1 Non-Polymeric Recyclable Hypervalent Iodine(III) Reagents3.2 Recyclable Non-Polymeric Hypervalent Iodine(V) Reagents3.3 Fluorous Hypervalent Iodine Reagents4 Ionic-Liquid/Ion-Supported Hypervalent Iodine Reagents5 Metal–Organic Framework (MOF)-Hybridized Hypervalent Iodine Reagents6 Conclusion

Porous architectures characterized by parallel channels arranged in honeycomb or rectangular patterns are identified in two polymorphic crystals of a zwitterionic 4-(aryliodonio)-benzenesulfonate. The channels are filled with disordered water molecules which can be reversibly removed on heating. Consistent with the remarkable strength and directionality of the halogen bonds (XBs) driving the crystal packing formation, the porous structure is stable and fully preserved on almost quantitative removal and readsorption of water. The porous systems described here are the first reported cases of one-component 3D organic frameworks whose assembly is driven by XB only (XOFs). These systems are a proof of concept for the ability of zwitterionic aryliodonium tectons in affording robust one-component 3D XOFs. The high directionality and strength of the XBs formed by these zwitterions and the geometrical constraints resulting from the tendency of their hypervalent iodine atoms to act as bidentate XB donors might be key factors in determining this ability.

University of Minnesota M.S. thesis. June 2021. Major: Chemistry. Advisors: Viktor Zhdankin, Akira Yoshimura. 1 computer file (PDF); vi, 93 pages.

2-Iodosylbenzoic acid in the presence of trifluoromethanesulfonic anhydride is an efficient oxidant and electrophilic reagent useful for preparation of the corresponding alkenyl and aryliodonium salts. Compared to the previously reported methods of electrophilic activation of 2-iodosylbenzoic acid, this procedure is compatible with acid-sensitive functional groups, requires mild reaction conditions, and affords products in higher yields.

Organohypervalent iodine reagents are widely used for the preparation of various oxazolines, oxazoles, isoxazolines, and isoxazoles. In the formation of these heterocyclic compounds, hypervalent iodine species can serve as the activating reagents for various substrates, as well as the heteroatom donor reagents. In recent research, both chemical and electrochemical approaches toward generation of hypervalent iodine species have been utilized. The in situ generated active species can react with appropriate substrates to give the corresponding heterocyclic products. In this short review, we summarize the hypervalent-iodine­-mediated preparation of oxazolines, oxazoles, isoxazolines, and isoxazoles starting from various substrates.1 Introduction2 Synthesis of Oxazolines3 Synthesis of Oxazoles4 Synthesis of Isoxazolines5 Synthesis of Isoxazoles6 Conclusion

This account describes the development of organosulfonyloxy-substituted iodine(III) and iodine(V) benziodoxole derived reagents, which are thermally stable compounds with useful reactivity patterns. Iodine(III) benziodoxoles and pseudobenziodoxoles are powerful electrophiles and mild oxidants toward various unsaturated compounds. In particular, pseudocyclic benziodoxole-derived triflate (IBA-OTf) is an efficient reagent for oxidative heteroannulation reactions. Aldoximes react with nitriles in the presence of IBA-OTf at room temperature to give 1,2,4-oxadiazoles in high yields. Moreover, IBA-triflate is used as a catalyst in oxidative heteroannulations with m-chloroperoxybenzoic acid as the terminal oxidant. The iodine(V) benziodoxole derived tosylates, DMP-tosylate and IBX-tosylate, are superior oxidants for the oxidation of structurally diverse, synthetically useful alcohols, utilized as key precursors in the total syntheses of polyketide antibiotics and terpenes. And finally, the most powerful hypervalent iodine(V) oxidant, 2-iodoxybenzoic acid ditriflate (IBX·2HOTf), is prepared by treatment of IBX with trifluoromethanesulfonic acid. According to the X-ray data, the I–OTf bonds in IBX-ditriflate have ionic character, leading to the high reactivity of this reagent in various oxidations. In particular, IBX-ditriflate can oxidize polyfluorinated primary alcohols, which are generally extremely resistant to oxidation.1 Introduction2 Iodine(III) Benziodoxole Based Organosulfonates3 Pseudocyclic Iodine(III) Benziodoxole Triflate (IBA-triflate)4 Pseudocyclic Iodine(III) Benziodoxole Tosylates5 Iodine(V) Benziodoxole Derived Tosylates6 Iodine(V) Benziodoxole Derived Triflate (IBX-ditriflate)7 Conclusions

The synthesis of substituted 1,4-benzoquinones, a biologically important class of compounds, was developed using μ-oxodi(phenyliodanyl) diacetate, a (diacetoxyiodo)benzene-based oxidizing reagent, in order to introduce second-year undergraduate organic laboratory students in their second semester or advanced organic students to increasingly popular and environmentally friendly hypervalent iodine chemistry. This experiment develops on concepts found in the undergraduate organic chemistry curriculum; conveniently fits into approximately two 3 h lab modules; and utilizes regularly found equipment and inexpensive, commercially available chemicals.

A ditriflate derivative of 2-iodoxybenzoic acid (IBX) was prepared by the reaction of IBX with trifluoromethanesulfonic acid and characterized by single crystal X-ray crystallography. IBX-ditriflate is the most powerful oxidant in a series of structurally similar IBX derivatives which is best illustrated by its ability to readily oxidize hydrocarbons and the oxidation resistant polyfluoroalcohols.

International audience; Covalent modification of graphene-based materials can be considered as one of the most promising methods for tailoring their electrochemical properties and extending their application as electrode materials for supercapacitors. In this contribution, we report a facile and mild approach for the covalent functionalization of reduced graphene oxide (rGO) via aryne cycloaddition using pseudocyclic iodoxoborole as an aryne source. The structure and chemical composition of the functionalized rGO (f-rGO) were assessed by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), ultraviolet-visible (UV-vis) spectrophotometry, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), which revealed the negligible influence of covalent modification on the rGO structure. Transmission electron microscopy (TEM) imaging showed an increase of the interlayer distance from 0.38 to 0.46 nm upon functionalization. The electrochemical performance of f-rGO material was studied by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) techniques in 2 M KOH aqueous solution as the electrolyte. Under optimized conditions, the f-rGO displayed a high specific capacitance of 297 F g-1 at a current density of 1 A g-1, which is much higher than that of unmodified rGO (170 F g-1 at 1 A g-1). Therefore, the f-rGO was used to construct a symmetric supercapacitor device, exhibiting an energy density of 6.7 Wh kg-1 at a power density of 685.8 W kg-1. The device exhibited good cycling stability and ability to maintain about 96% of the initial capacitance value after 10,000 cycles. Furthermore, two symmetric supercapacitor devices were successfully applied to power a home-designed windmill device for 3 s. The results obtained in the present study highlight the importance of graphene functionalization as an effective route to fabricate rGO-based materials with enhanced properties in energy storage devices.

A novel approach to the preparation of imidazole-substituted cyclic iodonium salts has been developed via the oxidative cyclization of 1-phenyl-5-iodoimidazole using a cheap and available Oxone/H2SO4 oxidative system. The structure of the new polycyclic heteroarenes has been confirmed by single-crystal X-ray diffractometry, revealing the characteristic structure features for cyclic iodonium salts. The newly produced imidazole-flanked cyclic iodonium compounds were found to readily engage in a heterocyclization reaction with elemental sulfur, affording benzo[5,1-b]imidazothiazoles in good yields., The heterocyclization study was supported by the Russian Science Foundation (project No. 17-73-20066). Y.A.V. kindly acknowledges the financial support from the Russian Foundation of Basic Research for the development of oxidative cyclization process (project No. 20-33-90007). This work was funded by Spain’s MINECO (CTQ2017-86936-P), AGAUR (2017 SGR 01051), and additional support from CSIC. The authors would like to acknowledge the Multi-Access Chemical Research Center SB RAS (N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry) and the Center for Chemical Analysis and Materials Research of Saint Petersburg State University for analytical measurements. X-ray structural results were obtained using the material and technical base of the Baikal Analytical Center for Collective Use of the SB RAS.

The selective preparation of 2-iodoxybenzenesulfonic acid (IBS, as potassium or sodium salts) by oxidation of sodium 2-iodobenzenesulfonate with Oxone or sodium periodate in water is reported. The single crystal X-ray diffraction analysis reveals a complex polymeric structure consisting of three units of IBS as potassium salt and one unit of 2-iodoxybenzenesulfonic acid linked together by relatively strong I=O···I intermolecular interactions. Furthermore, a new method for the preparation of the reduced form of IBS, 2-iodosylbenzenesulfonic acid, by using periodic acid as an oxidant, has been developed. It has been demonstrated that the oxidation of free 2-iodobenzenesulfonic acid under acidic conditions affords an iodine(III) heterocycle (2-iodosylbenzenesulfonic acid), while the oxidation of sodium 2-iodobenzenesulfonate in neutral aqueous solution gives the iodine(V) products.

A simple and convenient synthesis of ω-iodoaliphatic carboxylic acids and esters by the reaction of cyclic ketones with iodine and hydrogen peroxide in the presence of catalytic CuCl has been developed. ω-Iodoaliphatic carboxylic esters were further used for the efficient preparation of di(2-pyridylmethylamino)alkanoic acids in excellent yields.

A new bicyclic organohypervalent iodine heterocycle derivative of benziodazole was prepared by oxidation of 2-iodo-N,N’-diisopropylisophthalamide with m-chloroperoxybenzoic acid under mild conditions. Single crystal X-ray crystallography of this compound revealed a five-membered bis-heterocyclic structure with two covalent bonds between the iodine atom and the nitrogen atoms. This novel benziodazole is a very stable compound with good solubility in common organic solvents. This compound can be used as an efficient reagent for oxidatively assisted coupling of carboxylic acids with alcohols or amines to afford the corresponding esters or amides in moderate yields.

A facile synthesis of diaryliodonium salts utilizing Oxone as versatile and cheap oxidant has been developed. This method shows wide applicability and can be used for the preparation of iodonium salts containing electron-donating or electron-withdrawing groups in good yields. In addition, this procedure can be applied to the preparation of symmetric iodonium salts directly from arenes via a one-pot iodination–oxidation sequence.

New substituted 1-arylbenziodoxolones were prepared and their reactivity with azide anion nucleophile was investigated. It was found that independent on the presence of substituents, all reactions of 1-arylbenziodoxolones proceed as nucleophilic substitution of the iodonium leaving group in the electron-deficient benziodoxolone benzene ring. The presence of bulky substituents in the ortho-position of the aryl ring slowers the reaction, while the presence of a moderately electron-withdrawing bromine substituent in the para-position to iodine in the benziodoxolone ring moderately increases the rate of substitution. The presence of a strongly electron-withdrawing nitro group in the para-position to iodine in the benziodoxolone ring dramatically increases the rate of substitution. These observations are in agreement with the electronic requirements for internal nucleophilic substitution in the benziodoxole ring. A quantum-chemical computational study of the possible reaction paths is in agreement with the observed effects of substituents on the reactivity of arylbenziodoxolones in this reaction.

[Bis(trifluoroacetoxy)iodo]benzene (BTI) and (diacetoxyiodo)benzene (DIB) efficiently promote the formation of acylnitroso species from hydroxamic acids in the presence of various dienes to give the corresponding hetero-Diels–Alder (HDA) adducts in moderate to high yields. The present method could be applied to the HDA reactions of acylnitroso species with o-benzoquinones generated by the oxidative dearomatization of guaiacols.

Phenol based aryliodonium salts were prepared by the reaction of [hydroxy(tosyloxy)iodo]arenes with aryl silyl ethers in the presence of trifluoromethanesulfonic acid. Structures of several aryliodonium salts with the hydroxy group in the para-position of the phenyl ring were established by single crystal X-ray crystallography. Under basic conditions, 4-hydroxyphenyl(phenyl)iodonium salts form a dimeric hypervalent iodine(iii) complex, oxyphenyl(phenyl)iodonium ylidic salt, the solid structure of which was confirmed by X-ray crystallography. Phenolic iodonium salts are potentially useful phenol transfer reagents in reactions with various anionic nucleophiles.

The synthesis and characterization of a novel latent ruthenium catalyst bearing a chelate ligand containing an oxadiazole fragment for the olefin metathesis are described. The main advantages of the utilization of this ligand are the straightforwardness of preparation, mild reaction conditions, and availability of the feedstock. Preliminary study of the catalytic activity of the Ru complex for metathesis reactions demonstrated its inactive nature for the ring-closing metathesis (RCM), but an excellent thermo-switchability for the ring-opening metathesis polymerization of norbornene.