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Herein, nickel-catalyzed synthesis of polyarylcarbazole through sequential C-H bond activations has been described. Regioselective indole C2/C3 functionalization has been achieved in the presence of indole C7-H, which is quite challenging. In addition, this approach also gives easy access to building a heteropolycyclic motif through C6/C7 C-H functionalization of indoline. This methodology is not limited to aromatic internal alkynes as coupling partners; aliphatic alkynes have also shown good tolerance. Notably, during the optimization the catalytic enhancement with sodium iodide as an additive has been observed. We have also studied the photophysical properties of these highly conjugated molecules.

A series of novel heteroditopic halogen bonding (XB) receptor functionalised silica based materials, containing mono‐ and bis‐iodotriazole benzo‐15‐crown‐5 groups are investigated for the cooperative binding and extraction of sodium halide ion‐pair species from aqueous solution. Characterisation of the XB materials by CHN elemental analysis, 13C CP/MAS NMR and ATR‐FTIR spectroscopies confirms and quantifies the successful incorporation of the ion‐pair receptor frameworks to the silica material. ICP‐MS solid‐liquid extraction studies demonstrate the bidentate XB functionalised material is capable of NaI extraction from water. Importantly, cooperative XB‐mediated sodium halide ion‐pair binding is determined to be crucial to the material's extraction capabilities, impressively demonstrating a two‐fold enhancement in sodium iodide extraction efficiency relative to a heteroditopic hydrogen bonding receptor functionalised silica material analogue., A series of halogen bonding (XB) heteroditopic ion‐pair receptors comprising of benzo15‐crown‐5 cation binding moieties and iodotriazole XB donors are covalently integrated into silica QuadraSilTM based solid supports. Investigations into their sodium halide extraction capabilities demonstrated their ability as NaI extraction agents from water. Comparison with HB analogues demonstrate the crucial role of XB‐mediated NaI ion‐pair binding in the extraction performance.

A practical and efficient method to synthesize thiocarbamyl fluorides and isothiocyanates from amines with trifluoromethanesulfonyl chloride was developed. In the presence of the reducing agent triphenylphosphine and sodium iodide, thiocarbamyl fluorides and isothiocyanates were synthesized from secondary/primary amine in moderate to excellent yields, respectively. A broad scope of substrates and good functional group compatibility were observed.

An efficient photocatalytic dual decarboxylative alkenylation of α,β-unsaturated carboxylic acids and alkyl N-hydroxyphthalimide (NHP) esters mediated by triphenylphosphine and sodium iodide has been developed. This protocol proceeds under 456-nanometer irradiation by visible blue light in the absence of transition metals or organic dye based photoredox catalysts. The reaction is successfully applied to a wide range of redox-active esters derived from aliphatic carboxylic acids (1°, 2° and 3°) and α-amino acids, enabling transformations of diverse α,β-unsaturated carboxylic acids to α,β-alkylated styrenes with high efficiency and excellent selectivity under mild conditions.

By simple combination of water and sodium iodide (NaI) with chlorotrimethylsilane (TMSCl), promotion of a Vorbrüggen glycosylation en route to essential HIV drugs emtricitabine (FTC) and lamivudine (3TC) is achieved. TMSCl-NaI in wet solvent (0.1 M water) activates a 1,3-oxathiolanyl acetate donor for

Vinyl sulfides and vinyl sulfones are ubiquitous structures in organic chemistry because of their presence in natural and biologically active compounds and are very frequently encountered structural motifs in organic synthesis. Herein we report an efficient synthesis of vinyl sulfides and vinyl sulfones via transition metal-free sodium iodide-mediated sulfenylation of alcohols and sulfinic acids with solvent-controlled selectivity.

Regulating the aqueous polymerization of acrylic acid (AA) is a major opportunity for future materials design, requiring the development of scalable, industry‐oriented procedures that afford modest molar mass and dispersity control without long reaction times and environmentally demanding conditions. To address these challenges, this report presents the rapid copolymerization of aqueous mixtures of AA and sodium acrylate using an inexpensive and scalable protocol based on alkyl iodides/sodium iodide as mediators in water.

The utilization of sodium iodide, potassium persulfate, and a thermal radical initiator enables facile access to PAA via the direct reverse iodine transfer polymerization of acrylic acid. This polymerization proceeds rapidly in aqueous media using inexpensive and commercially available reagents.

Electrochemical oxidative radical sulfonylation/semipinacol rearrangement sequences of alkenylcyclobutanols have been developed. The reaction proceeds in an undivided electrochemical cell equipped with platinum plate electrodes employing sodium iodide as a redox catalyst and a supporting electrolyte. This approach is environmentally benign by using shelf-stable arylsulfonyl hydrazides as arylsulfonyl radical precursor and electrons as oxidizing reagents. The present protocol offers a facile way to prepare β-sulfonated cyclic ketone derivatives.

The usefulness of dried Dowex H+ cation-exchange resin with or without sodium iodide (NaI) as a catalyst system for different kinds of esterifications using carboxylic acids and alcohols as starting materials has been systematically investigated. The Dowex H+/NaI approach is very effective, generally high yielding, energy-efficient, and nontoxic, and the Dowex H+ resin is reusable. Since the whole procedure from start to product isolation is also very simple, these features make the method environmentally friendly. The method is regioselective, and its potential for separation of valuable carboxylic acids like resin acids from mixtures containing other kinds of carboxylic acids has been demonstrated. Examples for green and straightforward esterification of highly important natural amino acids are also presented.

Polymer brushes are known to form highly efficient lubricating layers for a broad range of contacting surfaces in water. Here we focus on brushes of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) polymers that are end-anchored to the substrate at a high density. We show that the friction coefficient, which is measured upon sliding atomic force microscopy colloid probes on PMPC brushes at different normal loads, decreases when salts are added (1 M sodium fluoride (NaF), sodium chloride (NaCl), sodium iodide (NaI), cesium chloride (CsCl) and cesium iodide (CsI)). Interestingly, we observe that the reduction in the friction coefficient increases with increasing anionic size in the solution, while the size of the cation has no measureable effect. We relate the reduction in the friction coefficient to a decrease in the compliance of the brush. In pure water the brush is swollen and soft, resulting in a large contact area between colloids and brushes and, therefore, a relatively “high” friction coefficient. In salt solutions, the stiffness of the brush increases with increasing anionic size resulting in a lower contact area and, therefore, lower friction coefficient.

We showed for the first time, the fundamental role of CH3CN associated to TMSCl/NaI combination to deprotect S,S-ethylene- and S,S-propylene-ketals into ketones. Indeed, if the TMSCl/NaI association leads to the reduction of dithioketals in CH2Cl2, we have demonstrated that this association can be used to deprotect a large variety of various dithioketals into ketones in CH3CN. Otherwise, under mild experimental conditions, O,O-acetals as well as O,S-oxathianes were cleanly deprotected with high yields. It is also possible to easily regenerate the carbonyl function of various hydrazones and imines using this novel protocol. We believe that this metal-free process is a good alternative to other known methodologies used to deprotect dithioketals into ketones.

An operationally simple sodium iodide-mediated C-S and C-Se bond formation protocol involving substituted 4-quinolone and thiols/diselenide to generate different ArS/ArSe-substituted 4-quinolone derivatives in excellent yields was developed. The versatility of this methodology has been successfully demonstrated by extension of the suitable reaction conditions to both substrates having different substituents. This regioselective C-H bond activation approach provides a direct access of structurally diverse 3-sulfenylated/selenylated 4-quinolone derivatives. Moreover, this new method proceeds without a transition-metal catalyst and prerequisite NH protection of 4-quinolone derivatives.

Poly(vinylpyrrolidone) (PVP) complexed with sodium iodide (NaI) is synthesized to investigate the ionic conductivity of alkaline-based polymer electrolytes. In this article, we report the modification of electrical properties of a new ion-conducting polymer electrolyte, namely, PVP complexed with NaI. Modification of polymer electrolyte was carried out before and after the exposure of films by bombarding them at different fluences with respect to Li3+ ion beam at 60 MeV. The preparation and detailed characterization of PVP:NaI is being reported. Further, a correlation with conductivity and dielectric constant has also been established. The modulation in the conductivity is explained in terms of number of charge carriers ( n) and its mobility ( μ), which confirms the behavior of the polymer electrolyte as an alternative strategy to improve the conductivity.

A convenient and economical one-pot synthesis of a series of new 1-aryl-substituted 4-iodopyrazole-3-ols from easily available pyrazolidin-3-ones in the presence of sodium iodide, 30% solution of hydrogen peroxide and a catalytic amount of sulfuric acid in dichloromethane via aromatisation and oxidative iodination reactions are described. This protocol has the advantages of high atom economy, cost-effectiveness, short reaction time and environmental friendliness.

The palladium-catalyzed direct C H diacetoxylation of pyrrolo[2,3-d]pyrimidine derivatives was realized in a mild, efficient and high regioselective manner. The amounts of sodium iodide is a critical factor for the unique regioselectivity of this catalytic system. A wide range of functional groups are tolerated in this protocol, which can be further modified and potentially of great importance in medicinal chemistry.

A strategy has been developed for constructing sulfenylated 2,3-dihydrobenzofurans and β-acetoxy sulfides through NaI/DMSO-­mediated oxysulfenylation of alkenes with environmentally friendly thiosulfates. The reactions involve simple operations and give a series of sulfenylated 2,3-dihydrobenzofurans or β-acetoxy sulfides in moderate to good yields.

A simple and practical NaI-catalyzed direct C-H sulfenylation of arenes has been developed under air. In this reaction, aryl sulfides were obtained in moderate to excellent yields with high regioselectivity from readily available aromatic compounds and aryl/alkyl thiols, even on gram scale. To demonstrate the practicability of this reaction, two bioactive compound skeletons were synthesized in good yields. This method can also be used to late-stage modification of curcumin.

The synthesis of monocyclic, spirocyclic and fused bicyclic secondary amines bearing a gem-difluorocyclopropane moiety via difluorocyclopropanation of unsaturated N-Boc derivatives using the trifluoromethyl(trimethyl)silane/sodium iodide [CF3SiMe3-NaI] system is described. The relative order of the substrate reactivity is established. It is shown that for the reactive alkenes the standard reaction conditions can be used, whereas for the substrates with low reactivity, slow addition of the Ruppert–Prakash reagent is necessary.

3-Arylthioindoles could be synthesized in good yields via the photoirradiation of indoles and disulfides. The reaction is efficiently promoted by the catalytic amount of sodium iodide. A reaction mechanism involving the electrophilic substitution of indoles with arylsulfenyl iodine intermediates is suggested.

Halogen exchange of alkyl bromide (R–Br) with sodium iodide (NaI) was used for the transformation of R–Br to alkyl iodide (R–I) in situ in organocatalyzed living radical polymerization (LRP). R–Br was employed as a starting compound (precursor), and the R–I formed in situ was employed as an initiating dormant species for the polymerization. The efficiency of the transformation significantly depends on the R group of R–Br. By the rational selection of the R group and reaction temperature along with the use of tetrabutylammonium iodide (Bu4NI) as a catalyst, low-polydispersity (Mw/Mn = 1.1–1.4) polymers were obtained with high conversions (e.g., 70–90%) in reasonably short periods of time (typically 3–10 h) in the polymerizations of methyl methacrylate, butyl acrylate, styrene, acrylonitrile, and functional methacrylates. Well-defined diblock and triblock copolymers and a chain-end functional polymer were also obtained. R–Br is generally much more stable than R–I upon storage. Various R–Br are commercially available. The use of simple, stable, and inexpensive R–Br as precursors of the dormant species is an attractive feature of this system. The high monomer versatility and the accessibility to a wide range of polymer structural designs demonstrated in this work show the capability of this system for use in a range of applications. Accepted version

Pyrrolo[1,2-a]indole and organosulfone are common structural motifs found in many pharmaceuticals. An efficient approach for the synthesis of 2-sulfonated 9H-pyrrolo[1,2-a]indoles via a NaI-catalyzed sulfonyl-radical-involved cascade cyclization–isomerization process is described. By using sodium iodide as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidant, various N-propargyl-substituted indoles and sulfonyl hydrazides are tolerated in this transformation, affording the corresponding products in moderate to good yields.

Sulfonyl chlorides were reduced to anhydrous sulfinate salts with magnesium under sonication. These sulfinates were alkylated to sulfones with alkyl chlorides in the presence of catalytic sodium iodide under sonication. A variety of aliphatic sulfones was efficiently prepared by this one-pot two-step procedure.

International audience; Aristolochic acids are biologically active and highly toxic secondary metabolites that recently became an important pharmacological tool for in vivo models of acute kidney disorders. Only aristolochic acid I and a mixture of aristolochic acids I and II are currently commercially available. A method based on the strong-ion exchange displacement mode in centrifugal partition chromatography was developed to extract and purify arictolochic acids, naturally present in Aristolochia bracteolata Lam. (Aristolochiaceae). The extraction and purification of aristolochic acids were performed at a flow rate of 2 mL min−1 in the descending mode by using the biphasic solvent system methyl-ter-butylether, acetone, methanol and water (3:1:1:3, v/v/v/v). Trioctylmethylammonium chloride (Aliquat 336®) was used as the anion exchanger in the organic stationary phase and sodium iodide as the displacer in the aqueous mobile phase. From 5 g of crude extract of A. bracteolata, 45.5 mg, 77.2 mg and 35.1 mg of aristolochic acids I, II and IIIa were obtained respectively with purities greater than 95%.

In this study potato and corn starch were subjected to oxidation, using sodium periodate, to obtain dialdehyde starch (DAS) containing different amount of aldehyde groups. The obtained modified starch samples have been characterized with chemical analysis, scanning electron microscopy (SEM) and ATR-FTIR spectroscopy. Then, the samples were exposed to polychromatic UV radiation and the course of photochemical reaction has been monitored with ATR-FTIR spectroscopy. The surface properties of the native and dialdehyde starch before and after UV-irradiation have been determined by contact angle measurements and calculation of surface free energy. The crystallinity of the samples has been estimated with X-ray diffraction (XRD). It has been proved that the dialdehyded corn starch contained a higher amount of functional groups was more photostable than the oxidized potato starch. Sodium iodide(V), firmly bound to DAS macromolecules, has been found to have a significant effect on the photooxidative degradation of the tested systems. In addition, the mechanism of photoinduced reactions in the dialdehyde starch has been proposed.

Aryl iodides are important precursors in synthetic chemistry that form carbon-carbon and carbon-heteroatom bonds. Most methods use transition-metal catalysts, which need to be scrupulously removed before the compounds can be used in the pharmaceutical and electronics industries, where only parts-per-million levels of transition metals are allowed. The aromatic Finkelstein iodination reaction is a powerful method of preparing valuable aryl iodides from cheap but less reactive aryl bromides and chlorides. This protocol describes a transition metal-free method for a photo-induced aromatic Finkelstein iodination reaction that is performed at room temperature (20 °C). With common aromatic bromides and sodium iodide (NaI) as the starting materials, as well as a catalytic amount of I2 as an additive, the corresponding aromatic iodides can be synthesized in yields ranging from 56 to 93% under UV light irradiation in the absence of any metal catalysts. Various functional groups such as nitrile, ester and amino can be tolerated, which will facilitate the further functionalization of the aromatic iodides. The procedure normally requires 38-40 h to complete.

Iodination of 2-[allyl(methallyl)sulfanyl]-6-(trifluoromethyl)pyrimidin-4(3H)-ones was accompanied by cyclization to 2,3-dihydro[1,3]thiazolo[3,2-a]pyrimidin-4-ium triiodides. 3-(Iodomethyl)-3-methyl- 7-oxo-5-(trifluoromethyl)-2,3-dihydro[1,3]thiazolo[3,2-a]pyrimidin-4-ium triiodide was reduced with sodium iodide to 3,3-dimethyl-7-oxo-5-(trifluoromethyl)-2,3-dihydro[1,3]thiazolo[3,2-a]pyrimidin-4-ium iodide.

A simple and rapid nonradioactive iodide labeling/radiolabeling method for peptides, using an inexpensive oxidizing agent such as sodium hypochlorite and a cyclic peptide, cRGDyK (cyclo Arg-Gly-Asp-d-Tyr-Lys), was developed in this work. Labeling reaction was optimized by conducting experiments under variable ratios of the reagents, the reaction times, and the pH. The study demonstrated that radiolabeling of the cyclic peptide was fast and pH independent. Monoiodinated and di-iodinated cRGDyK were formed under all conditions and varied with the ratio of the reagents and the reaction time. Total percent of the iodinated cRGDyK (monoiodinated and di-iodinated cRGDyK) varied between 44 and 100 depending on the reaction conditions. Excess cyclic peptide over equal molar ratio of sodium iodide and sodium hypochlorite yielded in predominant amounts of monoiodinated cRGDyK, ie, >60% under 2:1:1 ratio and ~88% under 5:1:1 ratio of cRGDyK:sodium iodide:sodium hypochlorite.

The sodium iodide/hydrogen peroxide-mediated oxidation/lactonization of indolepropionic acids was achieved, affording the corresponding spirocyclic oxindole-lactones in moderate to high yields. This metal-free procedure features mild reaction conditions, non-toxicity and easy handling, with hydrogen peroxide (H2O2) as a clean oxidant.

Brominated poly(lactic acid) (PLB) and brominated poly(lactic acid-co-glycolic acid) (PLGB) were synthesized by acid-catalyzed melt copolyesterifications of glycolic acid and/or lactic acid with 2-bromo-3-hydroxypropionic acid, which is a brominated constitutional isomer of lactic acid. Molecular weights up to Mn = 104 Da were achieved by adding diphenyl ether to the copolymerizations (100% w/v comonomer concentration) performed at 90–130 °C in vacuo. GPCPSt underestimates the molecular weight of PLB when it contains at least approximately 6 mol % brominated units. The bromine atoms of PLB5050 (MnPSt = 5.32 × 103 Da; absolute Mn ∼ 1.70 × 104 Da) were replaced quantitatively with iodide using sodium iodide in acetone at room temperature, with a modest decrease in the molecular weight (MnPSt = 4.62 × 103 Da). PLB was also reacted with 0.25 equiv of sodium azide in DMF at 0 °C to replace the corresponding amount of bromine atoms in 88% efficiency, again with a slight decrease in the apparent molecular weight...

The preparation and isolation of a variety of mono-, bis-, and heteroleptic mesoionic triazol-5-ylidene palladium(II) complexes is reported. Treatment of phenoxy functionalized triazolium salts [Bn-MIC(H)]+I− (1) and [Mes-MIC(H)]+I− (2) with half equivalent of palladium acetate, produced complexes 3 and 4 with a general structure of [(MIC)2Pd(I)2] as isomeric cis/trans mixtures. When the reaction of palladium acetate and the cationic precursors was carried out with equimolar amounts in presence of sodium iodide, the μ2-I2 bridged complexes 5 and 6 of the type [(MIC)PdI2]2 were obtained as unique products. Additionally, the preparation of the heteroleptic PEPPSI-type complexes ([Py(PdI2)MIC]) 7 and 8 was readily achieved by the thermal treatment of the triazolium precursors with PdCl2, K2CO3, and sodium iodide in pyridine. All complexes have been fully characterized by 1H and 13C NMR, FT-IR, elemental analysis, and in the case of 2, 3trans, 6, and 7 single crystal X-ray diffraction. Preliminary catalytic results with the palladium series established the enhanced performance of PEPPSI complexes 7 and 8 in the Buchwald-Hartwing catalyzed formation of C–N bonds between aryl halides and primary/secondary amines under mild reaction conditions.

An alternative method with temperature dependency for obtaining direct chemo-, regio- and diastereoselective monobenzylidene and β-hydroxy carbonyl derivatives has been developed. In the present work, an attempt has been made to synthesize a precursor containing an organometallic compound, trimethylsilyl chloride (TMSCl), and cyclododecanone (CDD). Unexpectedly, this precursor exhibited temperature dependent chemoselective structures. At 35–40 °C, in situ formation of super silyl groups (TTMSS) from trimethylsilyl chloride stabilized the positive charge on the α-corner (C) side (sterically hindered side) of the CH2 group (1b) in zwitterionic CDD, leading to monobenzylidene derivatives (enones). At −20 °C, interestingly, TMSCl stabilized silyl enol ethers, which in turn produced β-hydroxy carbonyl derivatives (Mukaiyama aldol products) in the α-less hindered (S) side (sterically less hindered side) of the CH2 group. When we tried the reaction with TTMSSH instead of TMSCl, we failed to get either enones or aldol addition products. Tris(trimethylsilyl)silane (TTMSSH) stabilized the positive charge on the α-less hindered (S) side of the CH2 group. In the present protocol, the formation of monobenzylidene derivatives occurred in one step, whereas the methods available so far involved more than three steps. From this, it is clear that temperature is the only factor that changes the course of the reaction. In order to achieve diastereoselectivity in the Mukaiyama aldol reaction, sodium iodide was added. In monobenzylidene derivatives, the E-isomer is predominant (97–99%), while in the case of Mukaiyama aldol products, the anti-isomer is predominant (85–99%).

A photoinduced radical cyclization of benzene-tethered 1,7-enynes with Togni reagent in the presence of sodium iodide is developed. Under ultraviolet irradiation, (Z)-4-(iodomethylene)-3-(2,2,2-trifluoroethyl)-3,4-dihydroquinolin-2(1H)-ones are generated in moderate to good yields. The transformation works well without any metals or photo-redox catalysts at room temperature. During the reaction process, the reaction proceeds through a trifluoromethyl radical-triggered α,β-conjugated addition/intramolecular 6-exo cyclization/iodination, with the formation of multiple bonds. Good functional group tolerance is observed under the reaction conditions.

A reaction of iron(III) chloride with sodium iodide was used to generate iodine for an innovative take on electrophilic cyclization. With ethanol as solvent, the reaction was observed to provide ideal conditions for iodocyclization of 2-alkynylthioanisoles. The fundamental step allows formation of iodine which becomes free to undergo reaction with the starting alkyne to yield the cyclized product. Implementing environmentally benign and simple chemistry, 2-iodosubstituted benzo[b]thiophenes were synthesized in high yields to produce an interesting display of useful molecules.

International audience; The palladium-mediated C–H radio-iodination of arenes using sodium iodide as the primary isotopic source is reported and performed without chemical know-how in 30 min and applied to the synthesis of complex radio-iodinated compounds of biological interest.

Novel nido-carboranyl azide [7-N3CH2CH2OCH2CH2O-7,8-C2B9H11]- was prepared by the reaction of 1-hydroxy-ortho-carborane with bis(2-chloroethyl) ether followed by the conversion to its nido-form and reactions with sodium iodide and sodium azide. Previously undescribed carboranyl azides 1-N3CH2CH2OCH2CH2S-1,2-C2B10H11 and [7-N3CH2CH2OCH2CH2S-7,8-C2B9H11]- were synthesized by alkylation of trimethylammonium salt of 1-mercapto-ortho-carborane with bis(2-chloroethyl) ether followed by reactions with sodium iodide and with sodium azide and by the conversion of closo-derivative to water soluble nido-form. closo- and nido-Carboranyl azides 1-N3CH2CH2OCH2CH2S-1,2-C2B10H11 and [7-N3CH2CH2OCH2CH2S-7,8-C2B9H11]- were used for the copper(I)-catalyzed azide-alkyne cycloaddition with phenyacetylene. The compounds prepared can be used for the copper(I)-catalyzed сonjugation with biomolecules that act as tumor-targeting vectors for radionuclide diagnostics and boron neutron capture therapy of cancer.

Marine aerosols consist of a variety of compounds and play an important role in many atmospheric processes. In the present study, sodium iodide clusters with their simple isotope pattern serve as model systems for laboratory studies to investigate the role of iodide in the photochemical processing of sea‐salt aerosols. Salt clusters doped with camphor, formate and pyruvate are studied in a Fourier transform ion cyclotron resonance mass spectrometer (FT‐ICR MS) coupled to a tunable laser system in both UV and IR range. The analysis is supported by ab initio calculations of absorption spectra and energetics of dissociative channels. We provide quantitative analysis of IRMPD measurements by reconstructing one‐photon spectra and comparing them with the calculated ones. While neutral camphor is adsorbed on the cluster surface, the formate and pyruvate ions replace an iodide ion. The photodissociation spectra revealed several wavelength‐specific fragmentation pathways, including the carbon dioxide radical anion formed by photolysis of pyruvate. Camphor and pyruvate doped clusters absorb in the spectral region above 290 nm, which is relevant for tropospheric photochemistry, leading to internal conversion followed by intramolecular vibrational redistribution, which leads to decomposition of the cluster. Potential photodissociation products of pyruvate in the actinic region may be formed with a cross section of

The selective and sensitive determination of potential genotoxic methanesulfonate impurities in drug substances is highly challenging. A new method is reported for testing of methyl methanesulfonate (MMS), ethyl methanesulfonate (EMS) and isopropyl methanesulfonate (IPMS) in active pharmaceutical ingredients (APIs). Headspace single drop microextraction (HS-SDME) with room-temperature ionic liquid (RTIL) as extractant was employed to preconcentrate analytes and eliminate the drug matrix simultaneously. In order to increase volatilities for HS extraction and to improve their reactivity of the further derivatization at the same time, sodium iodide (NaI) was added to the sample to derivatize methanesulfonates to the corresponding iodoalkanes. The iodoalkanes in the extract were derivatized with N, N-diethyldithiocarbamate (DDTC) after HS-SDME, followed by separation and detection with high-performance liquid chromatography with ultraviolet detection (HPLC-UV). Several important parameters, including reaction temperature, reaction time and concentration of NaI, sample volume, microdrop volume, stirring rate, salt addition, extraction time, concentration, reaction time and reaction temperature of DDTC were investigated. Under the optimal conditions, LODs and LOQs of all methanesulfonates were 15 ng mL−1 and 40 ng mL−1, respectively. Linearity (correlation coefficient values r > 0.999) and precision (the relative standard deviations were 1.0–4.6%) of six repeated injections were obtained. The recoveries at three spiked concentration levels were all in the range of 86.2–107.5% with the relative standard deviations

A catalytic enantioselective Mannich-type reaction of a cyclohexanone-derived alkenyl trichloroacetate with isatin imines was achieved using an (S)-BINOL-derived chiral tin dibromide possessing a 4-tert-butylphenyl group at 3- and 3′-positions as the chiral precatalyst in the presence of sodium methoxide, sodium iodide, and methanol. Optically active 3-alkylated 3-amino-2-oxindoles having up to 90% enantiomeric excess were diastereoselectively obtained in high yields under the influence of the in situ generated chiral tin iodide methoxide.

A method for the iododifluoromethylation of aromatic aldehydes using (bromodifluoromethyl)trimethylsilane (Me3SiCF2Br) is described. The selective formation of the CF2I group is based on using sodium iodide, with the sodium serving as a scavenger of bromide and iodide serving as a nucleophile with respect to difluorocarbene. The primary CF2I-addition products can undergo HI-elimination or iodine/zinc exchange followed by allylation in a one-pot manner.

A highly efficient and green protocol is reported for the reductive deoxygenation of organic epoxides to olefins using tin(II) chloride/sodium iodide as a novel reagent. The reaction gives an excellent yield (85–96%) in ethanol under reflux within 2–10 minutes, without affecting other functional groups. The advantages of our method are the use of inexpensive reagents, the eco-friendly and green reaction conditions, and the short reaction times and high yields.

The reaction of tellurium tetrahalides, TeX4 (X Cl. Br) with acetyltrimethylsilane in CCl4 at ambient temperature, unlike that of the aryltellurium trichlorides, ArTeCl3 that give the expected electrophilic substitution products, Ar(Me3SiCOCH2)TeCl2, (Ar = 1-C10H7, 2; 2,4,6-Me3C6H2, 3), afforded novel silylated heterocycles, 3-methyl-5-(trimethylsilyl)-1,2-oxatellurol-1-ium halides 1a and 1b. These Te(II) heterocyclic compounds undergo halide exchange with sodium iodide and also add dihalogens oxidatively to afford the corresponding iodide, 1c and the Te(IV) trihalides, 5a and 5b respectively. A large lowering of ν(CO) is indicative of strong Te⋯O C interactions among these heterocycles, and is also substantiated by single-crystal X-ray diffraction data for 3-methyl-5-(trimethylsilyl)-1,2-oxatellurol-1-ium chloride. The 125Te chemical shifts for the new 10-Te-3 telluranes and 12-Te-5 pertelluranes that involve tellurium bound to two highly electronegative atoms (O, X) are among the highest (downfield) reported for organotellurium(II) and (IV) compounds.

The functionalization of polymers with phosphorus based reagents is of great interest in the preparation of polymeric materials. In this work we present a straightforward method for the introduction of pendant diethyl phosphate groups into polyglycidol by reaction with diethyl chlorophosphate. The degree of functionalization was controlled by the ratio of the phosphorus reagent to the hydroxyl groups attached to the polyether backbone. Resulting polymers were characterized by 1H, 13C, 31P {1H} NMR spectroscopy, FTIR spectroscopy and SEC analysis. The removal of one and both ethyl groups of the phosphate ester was selectively achieved by reaction with sodium iodide or bromotrimethylsilane, respectively.

Treatment of levoglucosenone and some its derivatives with chloro(trimethyl)silane and sodium iodide in acetonitrile leads to opening of the 1,6-anhydro bridge and simultaneous reduction of the pyranose ring to pyran.