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It has been common practice to use tert-butyl nitrite (TBN) as a source of nitrogen, oxygen, or nitric oxide. In our current work, for the first time to the best of our knowledge, TBN was used as a source of carbon for N-tert-butyl amides synthesis.

All Fenton reagent-assisted DMSO activation and in situ ˙CH3-radical production reported yet exclusively employ homogeneous reagent systems. However, the method described herein is based on the use of a heterogeneous photo-Fenton-like system.

A room-temperature technique for the synthesis of 3-nitro-4-arylcoumarins is reported employing a persulfate-nitrogen doped graphene mixture in a watery medium as an oxidant.

The reaction was initiated by the photochemical activity of an electron donor–acceptor complex formed by the interaction of isocyanobiaryls with alkyl(aryl)sulfinates.

The 9,10-phenanthrenedione (PQ) visible-light photocatalysis for the construction of a series of trifluoromethylated benzoxazines in good to excellent yields has been developed by using N-(2-vinylphenyl)amides and trifluoromethylsulfinate as precursors. A plausible mechanism for the reaction is reported. It involves the oxidative difunctionalization of N-(2-vinylphenyl)amides through cascade C-O and C-C bond formations. This novel and operationally simple methodology featured with diverse functional group tolerance, is transition-metal-free, cost-effective, and operates in an open environment.

By using DDQ visible-light photocatalysis, an olefin-free method for the production of buta-1,3-dienes is disclosed. DDQ* converts alkylbenzenes to olefins and then olefins to buta-1,3-dienes in a consecutive manner.

The one‐electron oxidizing capacity of 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) improves significantly by visible‐light excitation. The exited‐state DDQ (DDQ*) even converts benzene, fluoroarenes, heteroarenes, benzyls and olefins into their corresponding radical cations as well as chloride and other anions into their radicals. These reactive intermediates have been utilized for the generation of C‐C and C‐X (N, O, or Cl) bonds in the synthesis of valuable organic compounds and natural products. This mini review provides an overview of such DDQ*‐initiated organic transformations with their scope and limitations and discusses the proposed reactions mechanisms.

Peroxodisulfate-assisted three-component benzylation of coumarins with styrenes and KSCN to 3-(1-aryl-2-thiocyanatoethyl)-2H-chromen-2-one is reported for the first time. This reaction proceeds via the consecutive addition of the SCN radical to styrenes followed by the addition of the resultant substituted-benzylic radical to the C3-position of coumarin derivatives. In contrast to previous approaches that normally require transition-metal catalysis, toxic volatile organic solvents, bases and elevated temperature, the present strategy of benzylation of coumarins is transition-metal-free and base-free, and applicable under ambient conditions with ethyl lactate as a green medium.

A series of 2,4-aryl-4-((arylsulfonyl)methyl)-4H-benzo[d][1,3]oxazines in good to excellent yields have directly been obtained from N-(2-vinylphenyl)amides and thiols by employing a mixture of K2S2O8-activated charcoal in aqueous acetonitrile solution at 50 °C. A plausible mechanism for the reaction is reported. It reveals that the reaction follows a radical pathway and the persulfate has been the oxygen source for formation of the sulfone group in the products. It is worth mentioning that this protocol utilizes an easily accessible K2S2O8-activated charcoal mixture and thiols, respectively, as an oxidant and sulfonylating precursors for the first time.

The binding dynamics of the trans-1-methyl-4-(4-hydroxystyryl)pyridinium cation (HSP⁺) to cucurbit[6]uril (CB[6]) in the presence of Na⁺ cations were studied to establish the effect of the relative concentrations of the system’s components (HSP⁺, CB[6], and Na⁺) on these dynamics. The formation of the HSP⁺@CB[6] complex was temporally uncoupled from the photoisomerization of trans-HSP⁺, while a nonlinear effect of the Na⁺ cation concentration on the HSP⁺@CB[6] dynamics was observed. This nonlinearity is a consequence of Na⁺ having the opposite effect on the association and dissociation rate constants for the HSP⁺@CB[6] complex, creating a conceptual framework for using such nonlinearities to control multistep reactions in cucurbit[n]uril chemistry.

This study targets the construction of metalloporphyrin assemblies directed by fluorine-centered non-covalent interactions that can conveniently operate on a metallated tetrapyridylporphyrin system, which topologically resembles a wheel–axle duo. We chose a series of Sn(axial-L)2-(5,10,15,20-tetrapyridylporphyrin) [Sn(L)2-TPyP, where L = fluorine-substituted benzoate moiety] complexes as our building units, which have only one fluorine atom on the benzoate moiety (compounds 1 and 2) but progressively increased to 2 (compound 3) and to 5 (compound 4). This stepwise augmentation also showed a concomitant increase in fluorine-based intermolecular interactions. Four complexes with varying F : H ratios of 1 : 4 to 5 : 0 at the axle part of the molecule were structurally analyzed by single-crystal X-ray diffraction. Fluorine-centered intermolecular interactions have been investigated and found to correlate with the number of fluorine atoms present at the axial benzoato-ligand of the wheel–axle duo. The augmentation in the number of fluorine-centered interactions was theoretically supported by Hirshfeld surface analysis showing a steep increase from 11% (1/2) to 20% (3) to 39% (4) as a function of the degree of fluorine-substitution. However, electrostatic potential surface (ESP) analysis clearly disproves the formation of σ-holes at fluorine atoms and thus vitiates their role as XB donors in these complexes. The occurrence of such short-contacts as a result of the ‘Gulliver effect’ should not be ruled out in fluorine based crystal engineering attempts.

An eco-friendly and a simple ipso-nitration protocol for a series of aliphatic and (hetero)aromatic carboxylic acids using nitronium tetrafluoroborate, 1-hexyl-3,4,5-trimethyl-1H-imidazolium tetrafluoroborate and base is reported. While contrasted with recently known decarboxylative ipso-nitration strategies for the preparation of nitro compounds, this protocol does not require a toxic metal catalyst and harmful volatile organic solvents. Moreover, this method is perfect for a broad range of functional groups and affords exclusively the ipso-nitrated product in moderate to good yields.

A series of 2,4-aryl-4-((arylsulfonyl)methyl)-4

The binding dynamics of the

The present study is devoted towards the construction of metalloporphyrin assemblies directed and sustained by halogen bonds (XBs) on judiciously selected molecular scaffolds. We choose a series of Sn(axial-L)2–(5,10,15,20-tetraiodoporphyrin) [Sn(L)2–TIPP, where L = halogen/nitro-substituted benzoate moiety] complexes as our building units that resemble a ‘wheel and axle’ topology aiding the construction of different types of molecular assemblies like ladder, 1D and 2D networks. In all the complexes explored herein, the wheel is constructed with Sn(IV)–5,10,15,20-meso-tetrakis(4-iodophenyl)porphyrin [Sn(L)2–TIPP], which is rigid and the two pairs of iodine atoms present at the meso-phenyl position of the porphyrin ring can get involved in XB interactions, depending upon the complementary interacting atoms present at the axle. Single crystal X-ray diffraction analysis confirms the occurrence of halogen bonds in crystalline metalloporphyrin assemblies via I⋯I, I⋯O and I⋯π halogen bonds. Most interestingly, these XBs are not only restricted between wheel⋯axle alone, but can also occur between wheel⋯wheel and axle⋯axle. Different types of XB-directed molecular associations are observed, for example, ladder-type supramolecular associations occur in 1, 2D-networks in 2, 3 and 8, interlinked 1D networks in 4 and 5, and 1D-networks in 7. Theoretical studies with Hirshfeld surface analysis show the definite role of XB interactions in the overall stability of the complexes. Electrostatic potential surface studies with the aid of density functional theory (DFT) in 2 and 8 show the presence of a σ-hole on the cap of the iodine atom which further augments the role of XBs in the observed architectures. The structural and theoretical studies presented here showcase that it is necessary to consider an adequate topology such as that of a ‘wheel and axle’ along with complementary interacting functional groups placed adequately on hexa-coordinated Sn(IV)–porphyrins to realize molecular constructions such as ladder, 1D and 2D networks.

A visible-light-mediated dehydrogenative homocoupling reaction of readily available mono- and disubstituted olefins to afford symmetrical di- and tetrasubstituted buta-1,3-dienes in the presence of catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) has been developed. The reaction proceeds for a wide range of substrates giving buta-1,3-dienes in moderate to good yields. We propose a reaction mechanism involving direct oxidative radical coupling followed by proton and hydrogen atom elimination.

A novel, visible-light-mediated method for the construction of 2-substituted benzothiazoles from easily available thiophenols (2.0 equiv.) and alkyl/aryl nitriles (1.0 equiv.) in the presence of eosin Y (0.02 equiv.) under air atmosphere has been developed. The reaction proceeded smoothly, for a wide range of derivatives of thiophenols and nitriles, to give the expected products in moderate to good yields. A reaction mechanism involves the direct oxidative radical coupling of thiophenols with nitriles to afford iminyl radical intermediates giving the expected product by an intramolecular cyclization followed by hydrogen radical loss. To the best of our knowledge, this is the first example of the synthesis of 2-substituted benzothiazoles through sequential C–S and C–N bond formation reactions under photoredox catalysis.

The C-H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH₂ as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimide and urea. Preliminary mechanistic investigations indicate a charge transfer complex between the amine and DDQ as essential intermediate of the reaction. The reactivity of amines and arenes in the photocatalytic reaction is therefore predictable from simple UV measurements.

Since the seminal studies from the groups of MacMillan, Stephenson and Yoon, visible light (400-700 nm) photoredox catalysis has been established as a powerful strategy to facilitate activation of organic molecules and invention of novel synthetic methodologies. Indeed, recent days, this protocol enables the syntheses of diversely functionalized organic molecules such as coerulescines, pseudotabersonines, drugs, agro chemicals, etc. Generally, activation of the redox-active functional groups of the radical precursors including diazonium salts, iodoniumsalts, sulfoniumsalts, phosphate esters, amines and sulfonyl chlorides is achieved via single-electron transfer from a photocatalyst excited by visible light irradiation sources. To date, some important reviews are available that summarize the visible light photoredox catalyses of various classes of organic compounds. To the best of our knowledge, however, there is still no review article exclusively discourses about the visible light induced productions and applications of radical species of sulfonyl chlorides (AASO2Cl, AA=alkyl/aryl). Therefore, in this review, we provide an overview on the visible light assisted procedures employed for the production of radical intermediates from sulfonyl chlorides. In addition, here we account the applications of these radical species in the syntheses of bi(hetero)aryls, difluoromethyl lactones, difluoromethyl pyrrolidines, polycyclic aromatic compounds, sulfones, trifluoromethyl (hetero)aryls, α-trifluoromethyl ketones and so on.

A mild, efficient and straightforward visible-light-driven method has been developed to construct 1,2-diarylvinyl sulfides under catalyst- and additive-free conditions. The formation of small amounts of thiyl radicals under visible light irradiation allows the synthesis of 1,2-diarylvinyl sulfides in good yield with an excellent functional group tolerance.

A novel visible-light (blue LEDs: hν = 425 ± 15 nm) photocatalyzed one-pot method for the synthesis of electronically diverse aryl glyoxals in good to excellent yields from acetoarylones and green regents such as air, vitamin C and dioxane dibromide has been described. In addition, an application of the current methodology has been demonstrated for the oxidation of monoamine oxidase-B inhibitors, i.e., 1-(4-((4-fluorobenzyl)oxy)phenyl)ethanone and 1-(3-((4-chlorobenzyl)oxy)phenyl)ethanone. This finding may serves as a valuable alternative to the traditional acetoarylones oxidation reactions conducted using selenium dioxide a harmful and unselective reagent known to simultaneously oxidize allylic, benzylic, CH3 and so on.

An atom-economical and environmentally benign approach for the synthesis of N-substituted carbazoles from analogous 2-aminobiaryls using peroxodisulfate in water is reported. The reactions proceeded through an intramolecular oxidative radical cyclization of N-substituted 2-aminobiaryls with in situ reoxidation of the resulting radical species. When compared to known methods for the synthesis of N-substituted carbazoles from 2-amidobiaryls, this protocol is practical, efficient and does not require a transition metal catalyst or toxic organic solvents.

Host—guest complexation with cucurbit[7]uril of anthocyanin model compounds in which acid—base equilibria are blocked resulted in essentially complete stabilization of their color. The color protection is a thermodynamic effect and establishes a strategy to stabilize these colored compounds at pH values of interest for practical applications.

Visible-light (Blue LED lamp: hν=425±15 nm) photocatalyzed cross-coupling reactions of arylsulfonyl chloride with N-methylpyrrole, furan, thiophene and their derivatives have been achieved in moderate to good yields at room temperature. A plausible mechanism has been proposed for the reaction. The arylation takes place at the C–H bond (C2–H or C5–H) next to the heteroatom with a high regioselective manner! Moreover, arylsulfonyl chlorides utilized in this study are inexpensive, environmentally benign and relatively more stable towards temperature, moisture and air as compared to diazonium salts normally used as coupling partners in the previously reported methods for the synthesis of heterobiaryls through visible-light photocatalyzed conditions.

A novel method is developed for the oxidation of thiols to the corresponding disulfides using 20 mol % haloacid (HBr or HI) in combination with dimethyl sulfoxide. A tentative mechanism is proposed for the oxidation. In addition to the advantages of cost-effectiveness, simple processes, and broad functional group tolerance, the exclusive formation of disulfides is the principle reward of this methodology while compared to known methods that further oxidize disulfides to S-oxides and other byproducts.

A new method is described for the oxidation of aliphatic- and aromatic disulfides containing electron-donating and electron-withdrawing groups to their corresponding thiosulfonates using oxone in combination with the MX (MX = KBr, KCl, NaBr and NaCl). No obvious electronic effects influence the yields of thiosulfonates. Avoiding the usage of toxic and unstable reagents, mild reaction conditions, short reaction times and cost-effectiveness are advantages of this methodology when likened to known methods for thiosulfonates syntheses.

Based on structural studies already available for the cocrystals of a sterically-rigidified tetraarylpyrene (TP) host substituted at the periphery by flexible methoxymethyl (MM) groups, i.e., TPMM, with aliphatic guests, formation of ternary or three-component cocrystals was targeted by replacing one of the guest species in the binary cocrystals with a different guest. Ternary cocrystals of TPMM with cyclododecene + cyclodecane, cyclododecene + cyclooctane and cyclododecene + decalin pairs were indeed successfully isolated and characterized by single-crystal X-ray structure determination. The ternary cocrystals, in principle, constitute ‘isomorphous pseudopolymorphs’ of binary cocrystals of TPMM with cyclododecene.

Indirect electrochemical synthesis of quinone derivatives of a series of substituted anthracene and naphthalene by the electrolysis of aqueous solution of potassium bromide (3.0 M) using Pt anode at constant current density (40 mA/cm 2 ) has been carried out. These reactions resulted in good to excellent yields of the corresponding para -quinones as confirmed by physical and spectral data.

A new method to synthesize 1,4-naphthoquinone and 9,10-anthraquinone from naphthalene and anthracene functionalized with either –CHO or –COOH groups, using N-bromosuccinimide (NBS) in aqueous N,N-dimethylformamide at 75–80 °C, has been developed. Further, –CN and –CONH2 functionalized naphthalenes and anthracenes can also be transformed into respective para-quinones in a one pot reaction, after successive acid hydrolysis and subsequent reaction with NBS. We believe that the present finding may serve as a valuable alternative to the classical approaches for the synthesis of polycyclic quinones from polyaromatic carbaldehydes through Dakin oxidation followed by further oxidation of the resulting hydroquinone by heavy metal oxides.

The concept of aggregation induced emission has been utilized to raise luminescence of triarylphosphines for the first time. Appreciable emission in the aggregated state as well as the Lewis basic character of these compounds were capitalized upon to demonstrate the functional utility as fluorescent chemosensors for elemental chlorine, Cl2, in aqueous solution.

To study the dual emission (from locally excited and charge transfer states) of sterically crowded 9,9'-bianthryl (BAHO) and its 10,10'-disubstituted derivatives, namely, 10,10'-dibromo-9,9'-bianthryl (BABR), 10,10'-bis(p-tolylethynyl)-9,9'-bianthryl (BAET), and 10,10'-bis(N,N-diphenyl-4-anilino)-9,9'-bianthryl (BATA) in detail, we probed their photophysical, redox, and electrogenerated chemiluminescence (ECL) responses. Dual emission for all of the molecules was noticed in PL, whereas in ECL only charge transfer emission was observed over a variety of experimental conditions. The PL in nonpolar solvents is significantly influenced by added supporting electrolyte, yielding exclusively charge transfer emission as in ECL. The stability of ECL proved to depend largely on the nature of the substituent, with triarylamine and bromo groups imparting constant ECL intensity over more than 60 cycles.

The dyads 1OFF and 2OFF were prepared by combining the inorganic luminophores [Ru(phen)2(2-[imidazol-2-yl]pyridine)](2+) and [Re(CO)3Cl(2-[imidazol-2-yl]pyridine)] with 2-(anthracen-9-yl)-4-methylphenol as a second photoactive moiety. In both cases, the inorganic unit operates as the emitter, whereas the organic part acts as a controller. Emission of the inorganic luminophore can be reversibly switched ON and OFF by adjusting the energetic level of the (3)π-π* state of the appended anthracene unit through either dearomatization using a photohydration or aromatization applying a thermal dehydration. Emission of both switches is reversibly recorded and erased multiple times without significant degradation.

Visible-light (Blue LED lamp: hν=425±15 nm) photocatalyzed cross-coupling reactions of arylsulfonyl chloride with N-methylpyrrole, furan, thiophene and their derivatives have been achieved in moderate to good yields at room temperature. A plausible mechanism has been proposed for the reaction. The arylation takes place at the C–H bond (C2–H or C5–H) next to the heteroatom with a high regioselective manner! Moreover, arylsulfonyl chlorides utilized in this study are inexpensive, environmentally benign and relatively more stable towards temperature, moisture and air as compared to diazonium salts normally used as coupling partners in the previously reported methods for the synthesis of heterobiaryls through visible-light photocatalyzed conditions.

Correction for ‘Cucurbit[7]uril inclusion complexation as a supramolecular strategy for color stabilization of anthocyanin model compounds’ by Barbara Held, et al., Photochem. Photobiol. Sci., 2016, DOI: 10.1039/c6pp00060f.

The D2d-symmetric bimesitylene core has been exploited for designing novel host materials required in the construction of phosphorescence-based organic light emitting devices. The oxadiazole-functionalized twisted bimesitylenes are found to exhibit high band gap (triplet energies), and excellent glass transition temperatures and thermal stabilities for ready exploitation as host materials. The electron-transporting ability and respectable luminance efficiencies with triplet dopants (up to 19.0 cd/A) allow oxadiazole-functionalized bimesitylenes as promising materials for phosphorescence-based light emitting devices, namely PHOLEDs.

The electrochemistry, spectroscopy, and electrogenerated chemiluminescence (ECL) of a variety of 2- and 4-fold anthracene-functionalized tetraarylbimesityls, AB1-4, were investigated. AB1-4 compounds contain a bimesityl core with 2- and 4-fold anthracene functionalities, which generate a rigid D(2d)-symmetric structure. Cyclic voltammetry of AB1 and AB2 showed two reversible, closely spaced one-electron transfers for both oxidation and reduction, and that of AB3 and AB4 showed four reversible, closely spaced one-electron transfers for oxidation and reduction in a benzene/acetonitrile solution. The multielectron transfer properties of all four compounds were confirmed by chronoamperometric experiments with an ultramicroelectrode and digital simulations. These serve as models to probe how interacting groups on a molecule affect the energies of successive electron transfers. AB1-4 compounds are highly fluorescent in nonaqueous solvents and display blue-green emission. They produce very strong ECL with emission at 480 nm, near that of the photoluminescence spectra that can be assigned to emission by direct formation of the singlet via the S-route.

The sterics introduced via methyl groups impart rigidity and inclusion behavior to trigonal C3-symmetric triphenol hosts H1–H4. Triphenol H1 is found to mimic the O–H···O hydrogen-bonded self-assembly of trimesic acid to yield porous honeycomb nets. It is found that 18-crown-6⊂H1 in turn binds guest molecules in the hexagonal voids to yield guest⊂guest⊂host multicomponent molecular crystals. The triphenol H2 and the homologous derivatives H3 and H4 are also found to crystallize with 18-crown-6 and other guests to yield multicomponent crystals, but in these cases the 18-crown-6 is found to serve as a spacer. While the structure of H2 is determined in its guest-free form, some of the inclusion compounds of triphenols lend themselves to crystal packings that are deciphered based on network topologies. The networks observed for H1–Tol and H3–C–B–Et are unique; in the latter, the crystal packing analysis reveals organization of molecules into a pattern that is reminiscent of borromean rings.

Sterically-engineered rigid trigonal molecular modules based on 1,3,5-tri(4-hydroxyphenyl)benzenes H1 and H2 undergo O-H...O hydrogen-bonded self-assembly into eight-fold catenated hexagonal (6,3) and two-fold interpenetrated undulated square (4,4) networks, respectively. In the presence of [18]crown-6 as a guest, the triphenol H1 is found to self-assemble into a honeycomb network with hexagonal voids created between three triphenol building blocks. The guest [18]crown-6 molecules are found to be nicely nested in hexagonal enclosures. The empty spaces within the crowns can be further filled with neutral (MeOH/water, MeOH/MeNO(2)) or ionic guest species such as KI/KAcAc to furnish novel multicomponent assemblies, that is, guest subset guest subset host, that typify Russian dolls. In contrast, triphenol H2 is found to yield analogous multicomponent molecular crystals in which the guest crown-K(+) acts as a spacers in the hydrogen-bonded self-assembly that leads to distorted chicken wire networks.

The twisted bimesitylene scaffold hinders crystallization and imparts amorphous nature to the oligophenylenevinylenes (OPVs) generated by 2- and/or 4-fold functionalization. The resultant phenylenevinylenes 1-5 with unique molecular topology exhibit excellent thermal and solid-state luminescence properties. The amorphous nature permits their application as pure-blue emissive materials in OLEDs. Under nondoped conditions, the device performances observed surpass those for analogous and simple oligophenylenevinylenes known so far; for example, the device based on OPV 2 as an emitting material and structurally analogous Bim-DPAB as a hole-transporting material yields pure-blue electroluminescence with an external quantum efficiency of ca. 4.70% at 20 mA/cm(2), which is higher than those reported for nondoped pure-blue OPV emitters.

The dicarboxylic acids 3 and 4, i.e., di(3-carboxy-2,4,6-trimethylphenyl)methane and di(3-carboxyphenyl)methane, are created by a methylene tethering of mesitoic acid and benzoic acid, respectively. These diacids may explore two low energy conformations, viz., syn and anti. Whereas the syn-diacid 3 is found to undergo self-assembly in the solid state via a very rare tetrameric motif, the anti-diacid 3 is found to exhibit pseudopolymorphism with guest molecules such as DMSO and PhOH-H 2 O. The unusual patterns of assembly and the occurrence of pseudopolymorphism for the syn and anti conformers, respectively, appear to emanate from an unique structural feature that emerges as a consequence of tethering. It appears that the molecules that contain strongly interacting functional groups in non-coplanar aryl rings will suffer from packing problems, which manifests itself in a new mode of packing and the phenomenon of pseudopolymorphism.

A novel method is developed for the oxidation of thiols to the corresponding disulfides using 20 mol % haloacid (HBr or HI) in combination with dimethyl sulfoxide. A tentative mechanism is proposed for the oxidation. In addition to the advantages of cost-effectiveness, simple processes, and broad functional group tolerance, the exclusive formation of disulfides is the principle reward of this methodology while compared to known methods that further oxidize disulfides to S-oxides and other byproducts.

A novel and efficient method for the regioselective nitration of a series of aliphatic and aromatic carboxylic acids to their corresponding nitro compounds using nitronium tetrafluoroborate and silver carbonate in dimethylacetamide has been described. This transformation is believed to proceed via the alkyl-silver or aryl-silver intermediate, which subsequently reacts with the nitronium ion to form nitro substances. Mild reaction conditions, tolerant of a broad range of functional groups, and formation of only the ipso-nitrated products are the key features of this methodology when compared to known methods for syntheses of nitroalkyls and nitroarenes.

A novel and efficient method for the regioselective nitration of a series of aliphatic and aromatic carboxylic acids to their corresponding nitro compounds using nitronium tetrafluoroborate and silver carbonate in dimethylacetamide has been described. This transformation is believed to proceed via the alkyl-silver or aryl-silver intermediate, which subsequently reacts with the nitronium ion to form nitro substances. Mild reaction conditions, tolerant of a broad range of functional groups, and formation of only the ipso-nitrated products are the key features of this methodology when compared to known methods for syntheses of nitroalkyls and nitroarenes.

A new method is described for the oxidation of aliphatic- and aromatic disulfides containing electron-donating and electron-withdrawing groups to their corresponding thiosulfonates using oxone in combination with the MX (MX = KBr, KCl, NaBr and NaCl). No obvious electronic effects influence the yields of thiosulfonates. Avoiding the usage of toxic and unstable reagents, mild reaction conditions, short reaction times and cost-effectiveness are advantages of this methodology when likened to known methods for thiosulfonates syntheses.