Oxidation of N-trifluoromethylthio sulfoximines using NaOCl·5H2O.

N-Trifluoromethylthio sulfoximines are biologically interesting compounds, but their potential is still poorly understood. The oxidation of N-trifluoromethylthio sulfoximines led to their corresponding sulfoxide derivatives as a new class of compounds, when using sodium hypochlorite pentahydrate (NaOCl·5H2O) as a green and relatively unexplored reagent. The reactions took place with a small excess of oxidant under environmentally friendly conditions in EtOAc for 16 h at room temperature. Noteworthy distinctions of this transformation are the simplicity, high selectivity, energy and cost efficiency, minimal amounts of non-hazardous waste, isolation of most of the products without the additional need for chromatographic purification, and simple scalability to gram reactions without deterioration of the yield. The reaction exhibited excellent green chemistry metrics with high atom economy (82.0%), actual atom economy (79.5%), reaction mass efficiency (79.7%), E-factor (16.48) and a very high EcoScale score (84.5). Competitive experiments demonstrated that electron-rich substrates are more reactive than their electron-poor counterparts. Furthermore, the Suzuki-Miyaura functionalization of N-trifluoromethylsulfaneylidene sulfoximine could be achieved depending on the conditions, resulting in coupling products with or without an introduced sulfoxide moiety. Sonogashira coupling of N-trifluoromethylsulfaneylidene sulfoximine furnished the expected acetylene derivative in high yield, and the reaction conditions are compatible with the newly introduced sulfaneylidene functionality. Bromine and nickel catalysts were also shown to be deprotecting agents of the sulfoxide group. A selected N-trifluoromethylsulfaneylidene sulfoximine demonstrated its stability in water in the presence of air and in dilute hydrochloric acid, while it converted back to the parent sulfoximine under basic conditions.

Sustainable and Selective Modern Methods of Noble Metal Recycling.

Noble metals exhibit broad arrange of applications in industry and several aspects of human life which are becoming more and more prevalent in modern times. Due to their limited sources and constantly and consistently expanding demand, recycling of secondary and waste materials must accompany the traditional mineral extractions. This Minireview covers the most recent solvometallurgical developments in regeneration of Pd, Pt, Rh, Ru, Ir, Os, Ag and Au with emphasis on sustainability and selectivity. Processing-by selective oxidative dissolution, reductive precipitation, solvent extraction, co-precipitation, membrane transfer and trapping to solid media-of eligible multi-metal substrates for recycling from waste printed circuit boards to end-of-life automotive catalysts are discussed. Outlook for possible future direction for noble metal recycling is proposed with emphasis on sustainable approaches.

Iodine-Catalysed Dissolution of Elemental Gold in Ethanol.

Gold is a scarce element in the Earth's crust but indispensable in modern electronic devices. New, sustainable methods of gold recycling are essential to meet the growing eco-social demand of gold. Here, we describe a simple, inexpensive, and environmentally benign dissolution of gold under mild conditions. Gold dissolves quantitatively in ethanol using 2-mercaptobenzimidazole as a ligand in the presence of a catalytic amount of iodine. Mechanistically, the dissolution of gold begins when I2 oxidizes Au0 and forms a [AuI I2 ]- species, which undergoes subsequent ligand-exchange reactions and forms a stable bis-ligand AuI complex. H2 O2 oxidizes free iodide and regenerated I2 returns back to the catalytic cycle. Addition of a reductant to the reaction mixture precipitates gold quantitatively and partially regenerates the ligand. We anticipate our work will open a new pathway to more sustainable metal recycling with the utilization of just catalytic amounts of reagents and green solvents.

One-Pot Synthesis of N-Iodo Sulfoximines from Sulfides.

This is the first report on the synthesis and characterization of N-iodo sulfoximines. The synthesis was designed as a room temperature one-pot cascade reaction from readily available sulfides as starting compounds, converted into sulfoximines by reaction with ammonium carbonate and (diacetoxyiodo)benzene, followed by iodination with N-iodosuccinimide or iodine in situ, in up to 90% isolated yields, also at a multigram scale. Iodination of aryls with N-iodo sulfoximines, oxidation, and conversion to N-SCF3 congeners have been demonstrated.

One pot synthesis of trifluoromethyl aryl sulfoxides by trifluoromethylthiolation of arenes and subsequent oxidation with hydrogen peroxide.

Hydrogen peroxide was used for oxidation of various aryl trifluoromethyl sulfides. Trifluoroacetic acid was used as an activating solvent that enables non-catalyzed oxidation and increases selectivity for sulfoxide formation. As shown by oxidation of thianthrene TFA enhances electrophilic character of the oxidant and further oxidation of sulfoxide group is blocked. We have joined trifluoromethylthiolation of arenes using a modified Billard reagent (p-ClPhNHSCF3) with oxidation of aryl trifluoromethyl sulfides using 1.2 equiv. of 30% aqueous hydrogen peroxide and this one-pot process has superior yields than would have been obtained in a two step process.

Iodine-catalyzed Transformation of Aryl-substituted Alcohols Under Solvent-free and Highly Concentrated Reaction Conditions.

Iodine-catalyzed transformations of alcohols under solvent-free reaction conditions (SFRC) and under highly concentrated reaction conditions (HCRC) in the presence of various solvents were studied in order to gain insight into the behavior of the reaction intermediates under these conditions. Dimerization, dehydration and substitution were the three types of transformations observed with benzylic alcohols. Dimerization and substitution reactions were predominant in the case of primary- and secondary alcohols, whereas dehydration prevailed in the case of tertiary alcohols. The relative reactivity of substituted 1-phenylethanols in I2-catalyzed dimerization under SFRC provided a good Hammett plot ρ+ = -2.8 (r2 = 0.98), suggesting the presence of electron-deficient intermediates with a certain degree of developed charge in the rate-determining step.

Acid-promoted direct electrophilic trifluoromethylthiolation of phenols.

The electrophilic aromatic ring trifluoromethylthiolation of various substituted phenols was accomplished using PhNHSCF3 (N-trifluoromethylsulfanyl)aniline, (1) in the presence of BF3·Et2O (2) or triflic acid as the promoter. The functionalization was exclusively para-selective; phenols unsubstituted in both the ortho- and para positions solely gave the para-substituted SCF3-products in all cases, while para-substituted phenols gave the ortho-substituted SCF3-products. 3,4-Dialkyl substituted phenols yielded the corresponding products according to the Mills-Nixon effect, and estrone and estradiol furnished biologically interesting SCF3-analogues. The highly reactive catechol and pyrogallol substrates gave the expected products smoothly in the presence of BF3·Et2O, whereas less reactive phenols required triflic acid. 2-Allylphenol gave the expected p-SCF3 analogue, which underwent an addition/cyclization sequence and furnished a new di-trifluoromethylthio substituted 2,3-dihydrobenzofuran derivative. Some additional transformations of 4-(trifluoromethylthio)phenol with NBS, NIS, HNO3, HNO3/H2SO4 and 4-bromobenzyl bromide were performed giving bromo-, iodo-, nitro- and benzyl substituted products. The latter derivative underwent Suzuki-Miyaura coupling with phenylboronic acid.

Iodine-catalyzed disproportionation of aryl-substituted ethers under solvent-free reaction conditions.

Iodine was demonstrated to be an efficient catalyst for disproportionation of aryl-substituted ethers under solvent-free reaction conditions. Variously substituted 1,1,1',1'-tetraaryldimethyl ethers were transformed into the corresponding diarylketone and diarylmethane derivatives. I2-catalyzed transformation of 4-methoxyphenyl substituted ethers yielded mono- and dialkylated Friedel-Crafts products as well. Treatment of trityl alkyl and trityl benzyl ethers with a catalytic amount of iodine produced triphenylmethane and the corresponding aldehydes and ketones. The electron-donating substituents facilitated the reaction, while the electron-withdrawing groups retarded it; the difference in reactivity is not very high. Such an observation may be in favour of hydride transfer, predominantly from the less electron rich side of the ether with more stable carbocation formation. With the isotopic studies it was established that a substantial portion of the C-H bond scission took place in the rate-determining step, while the carbonyl oxygen atom originated from the starting ether, and not from the air. The transformation took place under air and under argon, and HI was not a functioning catalyst.

Brønsted acidic ionic liquid accelerated halogenation of organic compounds with N-Halosuccinimides (NXS).

The Brønsted-acidic ionic liquid 1-methyl-3-(4-sulfobutyl)imidazolium triflate [BMIM(SO(3)H)][OTf] was demonstrated to act efficiently as solvent and catalyst for the halogenation of activated organic compounds with N-halosuccinimides (NXS) under mild conditions with short reaction times. Methyl aryl ketones were converted into α-halo and α,α-dihaloketones, depending on the quantity of NXS used. Ketones with activated aromatic rings were selectively halogenated, however in some cases mixtures of α-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO(3)H)][OTf] ionic liquid (IL-A) was successfully reused eight times in a representative monohalogenation reaction with no noticeable decrease in efficiency. An effective halogenation scale-up in this IL is also presented. The reactivity trend and the observed chemo- and regioselectiivities point to an ET process in these IL-promoted halofunctionalization reactions.

Ti(IV)-catalyzed asymmetric sulfenylation of 1,3-dicarbonyl compounds.

The electrophilic enantioselective sulfenylation of 1,3-dicarbonyl compounds with phenylsulfenyl chloride is effectively catalyzed by [Ti(TADDOLato)] complexes. The corresponding products are obtained in moderate to high yields. The highest ee values (up to 97 %) are obtained in toluene at room temperature and with a typical catalyst loading of 5 mol %. Bulky ester groups and sterically undemanding substituents at the alpha-position were found to be crucial structural features of the starting materials in order to assure high enantioselectivity. The absolute configuration of one of the chiral products has been determined. The stereochemical course of the reaction is similar to that of analogous [Ti(TADDOLato)]-catalyzed atom-transfer reactions. A common side-reaction the sulfenylated products undergo is a deacylation leading to racemic alpha-sulfenylated esters.

Titanium(IV)-catalyzed enantioselective sulfenylation of beta-ketoesters.

A [Ti(TADDOLato)] complex (1) catalyzes the enantioselective sulfenylation of beta-ketoesters using phenylsulfenyl chloride, giving ees of up to 88% and yields of up to 95%. The reaction does not require the presence of a base. [reaction: see text]

Selective and effective fluorination of organic compounds in water using Selectfluor F-TEDA-BF4.

[reaction: see text] Selective and effective fluorination of various types of organic compounds performed in water as the reaction medium using 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor F-TEDA-BF4) is reported. 2-Naphthole and 2-methoxynaphthalene were thus transformed to 1,1-difluoro-2(1H)naphthalenone, estrone to 10beta-fluoro-1,4-estradien-3,17-dione, phenyl-substituted alkenes to vicinal fluorohydrins, and various ketones, 1,3-diketones, or beta-ketoesters to corresponding alpha-fluoro or alpha,alpha-difluoro ketones.

Effective and selective iodofunctionalisation of organic molecules in water using the iodine-hydrogen peroxide tandem.

Efficient hydrogen peroxide enhanced iodofunctionalisation of ketones, 1,3-dicarbonyl derivatives and activated aromatic molecules using elemental iodine in water is achieved, whereas alkynes were stereoselectively converted into (E)-1,2-diiodoalkenes.

Selectfluor F-TEDA-BF4 mediated and solvent directed iodination of aryl alkyl ketones using elemental iodine.

Reactions of aryl alkyl ketones with methanol solution of elemental iodine and 1-fluoro-4-chloromethyl-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor F-TEDA-BF4) result in the formation of corresponding alpha-iodo ketones, while switch over of the regioselectivity can be directed by using acetonitrile as the solvent and selective iodination of the aromatic site of target molecules is thus achieved.