Base Metal Catalyzed Isocyanide Insertions

Isocyanides are diverse C₁ building blocks considering their potential to react with nucleophiles, electrophiles, and radicals. Therefore, perhaps not surprisingly, isocyanides are highly valuable as inputs for multicomponent reactions (MCRs) and other one‐pot cascade processes. In the field of organometallic chemistry, isocyanides typically serve as ligands for transition metals. The coordination of isocyanides to metal centers alters the electronic distribution of the isocyano moiety, and reaction pathways can therefore be accessed that are not possible in the absence of the metal. The tunable reactivity of the isocyanide functional group by transition metals has evolved into numerous useful applications. Especially palladium‐catalyzed isocyanide insertion processes have emerged as powerful reactions in the past decade. However, reports on the use of earth‐abundant and cheap base metals in these types of transformations are scarce and have received far less attention. In this Minireview, we focus on these emerging base metal catalyzed reactions and highlight their potential in synthetic organic chemistry. Although mechanistic studies are still scarce, we discuss distinct proposed catalytic cycles and categorize the literature according to 1) the (hetero)atom bound to and 2) the type of bonding with the transition metal in which the (formal) insertion occurs.     

Nickel-Catalyzed Sulfonylation of Aryl Bromides Enabled by Potassium Metabisulfite as a Uniquely Effective SO2 Surrogate

The development and mechanistic investigation of a nickel-catalyzed sulfonylation of aryl bromides is disclosed. The reaction proceeds in good yields for a variety of substrates and utilizes an inexpensive, stench-free, inorganic sulfur salt (K₂S₂O₅) as a uniquely effective SO₂ surrogate. The active oxidative addition complex was synthesized, isolated, and fully characterized by a combination of NMR spectroscopy and X-ray crystallography analysis. The use of the isolated oxidative addition complex in both stoichiometric and catalytic reactions revealed that SO₂ insertion occurs via dissolved SO₂, likely released upon thermal decomposition of K₂S₂O₅. Key to the success of the reaction is the role of K₂S₂O₅ as a reservoir of SO₂ that is slowly released, thus preventing catalyst poisoning.     

Systematische untersuchungen über das Verhalten von organozinnverbindungen gegenüber flüssigem schwefeldioxid IV. Reaktionen von alkenylstannanen mit flüssigem SO2

The behaviour of alkenyltin compounds toward liquid SO₂ under different conditions is investigated in this paper. Tetravinyltin gives a monosulfinate at low temperatures and a disulfinate at and above room temperature according to eqns. (1) and (2), respectively. Tetraallyltin always forms the unstable disulfinate which in the course of time decomposes into a polymeric product of composition (C₃H₅)₂Sn · 1.5 SO₂ according to eqn. (3). The trialkenyltin chlorides, R₃SnCl (R = vinyl, allyl) at room temperature take up 1 and 2 moles of SO₂, respectively, forming the corresponding insertion products R₂(RSO₂)SnCl [R = vinyl, eqn. (7)] and R(RSO₂)₂SnCl [R = allyl, eqn. (8)]. Divinyltin dichloride does not react with liquid SO₂ even at a temperature as high as 70°. Alkenyltin sulfinates are also obtained by metathetical reactions between alkenyltin chlorides and sodium sulfinates [eqns. (11) and (12)]. The IR and Raman spectra of the newly prepared compounds are discussed.     

Systematische untersuchungen über das verhalten von organozinn-verbindungen gegenüber flüssigem schwefel-dioxid : V. Reaktionen von perfluorierten organozinn-derivaten Mit SO2

To get a clear conception of the mechanism of SO₂ insertion into tin-carbon bonds, reactions of perfluorinated organotin compounds with liquid SO₂ were studied in detail. Of the pure perfluoroorgano derivativs (C₆F₅)₄Sn is completely inert, while (CF₂CF)₄Sn shows a slight reactivity. In mixed tetraorganotin compounds like (C₆H₅)₃SnC₆F₅ and (C₆H₅)₃SnCFCF₂ insertion takes place only into the tinphenyl bond. The case of (CH₃)₃SnC₆F₅ is interesting in so far that the presence of the C₆F₅ group deactivates the whole molecule towards attack by SO₂. Possible reasons for this effect are discussed. We also report on the synthesis of triphenyltin perfluoromethanesulfinate, (C₆H₅)₃SnO₂-SCF₃.     

Synthesis of Multifluoromethylated γ-Sultines by a Photoinduced Radical Addition–Polar Cyclization

Despite the significance of sultines in synthesis, medicine, and materials science, the chemistry of sultines has remained unexplored due to their inaccessibility. Herein, we demonstrate the development of a photoredox-catalyzed multifluoromethyl radical addition/SO₂ incorporation/polar cyclization cascade approach to multifluoromethylated γ-sultines. The reactions proceed by single electron transfer induced multifluoromethyl radical addition to an alkene followed by SO₂ incorporation, and single-electron reduction for polar 5-exo-tet cyclization. Key to the success of the protocol is the use of easily oxidizable multifluoroalkanesulfinates as bifunctional reagents. The reactions proceed with excellent functional-group tolerance to deliver γ-sultines in moderate to excellent yields.     

l-Proline-catalyzed five-component domino reaction leading to multifunctionalized 1,2,3,4-tetrahydropyridines

Multifunctionalized 1,2,3,4-tetrahydropyridines are concisely synthesized in good yields via l-proline-catalyzed or l-proline/FeCl₃-cocatalyzed one-pot multicomponent reactions (MCRs). The MCRs involve a domino hydroamination/prins reaction/Mannich-type reaction/intramolecular dehydration-cyclization process. The molecular structure of 5baa, one of multifunctionalized 1,2,3,4-tetrahydropyridines, was confirmed by single-crystal X-ray diffraction.     

Study on a stable destruction method of radioactive waste ion exchange resins

This paper is a study on a stable destruction method of radioactive waste ion exchange resins. According to the resin TGA results, its decomposition occurred through three stages. And a sufficient retention time of the resins and an effective retention capacity of SO₂ gases and the doped metal compounds were required to destruct resins doped with radioactive metals stably. The resins doped with radioactive metal surrogates were effectively destructed in the lab-scale MCO system. CO and SO₂ emissions were below 100 and 1 ppm, respectively. And the surrogates were collected more than 99.9% in the molten carbonate. Thus, the resins can be destructed stably in the MCO process.     

Automatic microanalyzers: VII. Automatic analyzer for rapid microdetermination of sulfur

A commercially available analyzer for determination of sulfur (0.5–100%) in organic and some inorganic compounds is described. It involves combustion of the sample at high temperature (1050 °C) to form SO₂ and SO₃ in a vertical reactor. SO₃ is reduced to SO₂ and nitrogen oxides to N₂ on copper at 850–900 °C. At this temperature the chemical reactions of SO₂ and copper are minimized so that SO₂ is obtained quantitatively in this range.Use of a vertical reactor and an autosampler makes an easy and complete automation of the sulfur determination possible. With this automation, great improvements are noticed in accuracy and precision over manual methods. The average time for a single determination is about 8 min.     

Structures and chemical reactions of SO2 adsorbates studied by surface XAFS

Adsorption and surface chemical reactions of SO₂ on Ni, Cu and Pd metal surfaces are studied by using surface XAFS, as well as XPS and STM. It has turned out that SO₂ lies flat on the Ni(100), Ni(110) and Ni(111) surfaces, while it stands on Pd(100) and Pd(111). By raising the temperature, surface reactions occur on these metal surfaces. Typical reactions on Ni and Cu are 3SO₂ → S+2SO₃, while those on Pd are 2SO₂ → S+SO₄. The structures of the adsorbate species are elucidated.     

Enhancing Capacity Performance by Utilizing the Redox Chemistry of the Electrolyte in a Dual‐Electrolyte Sodium‐Ion Battery

A strategy is described to increase charge storage in a dual electrolyte Na‐ion battery (DESIB) by combining the redox chemistry of the electrolyte with a Na⁺ ion de‐insertion/insertion cathode. Conventional electrolytes do not contribute to charge storage in battery systems, but redox‐active electrolytes augment this property via charge transfer reactions at the electrode–electrolyte interface. The capacity of the cathode combined with that provided by the electrolyte redox reaction thus increases overall charge storage. An aqueous sodium hexacyanoferrate (Na₄Fe(CN)₆) solution is employed as the redox‐active electrolyte (Na‐FC) and sodium nickel Prussian blue (Na_x‐NiBP) as the Na⁺ ion insertion/de‐insertion cathode. The capacity of DESIB with Na‐FC electrolyte is twice that of a battery using a conventional (Na₂SO₄) electrolyte. The use of redox‐active electrolytes in batteries of any kind is an efficient and scalable approach to develop advanced high‐energy‐density storage systems.     

The “Borrowing Hydrogen Strategy” by Supported Ruthenium Hydroxide Catalysts: Synthetic Scope of Symmetrically and Unsymmetrically Substituted Amines

The N‐alkylation of ammonia (or its surrogates, such as urea, NH₄HCO₃, and (NH₄)₂CO₃) and amines with alcohols, including primary and secondary alcohols, was efficiently promoted under anaerobic conditions by the easily prepared and inexpensive supported ruthenium hydroxide catalyst Ru(OH)_x/TiO₂. Various types of symmetrically and unsymmetrically substituted “tertiary” amines could be synthesized by the N‐alkylation of ammonia (or its surrogates) and amines with “primary” alcohols. On the other hand, the N‐alkylation of ammonia surrogates (i.e., urea and NH₄HCO₃) with “secondary” alcohols selectively produced the corresponding symmetrically substituted “secondary” amines, even in the presence of excess amounts of alcohols, which is likely due to the steric hindrance of the secondary alcohols and/or secondary amines produced. Under aerobic conditions, nitriles could be synthesized directly from alcohols and ammonia surrogates. The observed catalysis for the present N‐alkylation reactions was intrinsically heterogeneous, and the retrieved catalyst could be reused without any significant loss of catalytic performance. The present catalytic transformation would proceed through consecutive N‐alkylation reactions, in which alcohols act as alkylating reagents. On the basis of deuterium‐labeling experiments, the formation of the ruthenium dihydride species is suggested during the N‐alkylation reactions.     

A Low-Cost and Environmentally Friendly Mixed Polyanionic Cathode for Sodium-Ion Storage

Sodium-ion batteries (NIBs) are the most promising alternatives to lithium-ion batteries in the development of renewable energy sources. The advancement of NIBs depends on the exploration of new electrode materials and fundamental understanding of working mechanisms. Herein, via experimental and simulation methods, we develop a mixed polyanionic compound, Na₂Fe(C₂O₄)SO₄⋅H₂O, as a cathode for NIBs. Thanks to its rigid three dimensional framework and the combined inductive effects from oxalate and sulfate, it delivered reversible Na insertion/desertion at average discharging voltages of 3.5 and 3.1 V for 500 cycles with Coulombic efficiencies of ca. 99 %. In situ synchrotron X-ray measurements and DFT calculations demonstrate the Fe²⁺/Fe³⁺ redox reactions contribute to electron compensation during Na⁺ desertion/insertion. The study suggests mixed polyanionic frameworks may provide promising materials for Na ion storage with the merits of low cost and environmental friendliness.     

Theoretical studies on the alkylidene germylenoid H<Subscript>2</Subscript>C=GeLiF and its insertion reaction with R-H (R = F,OH, NH<Subscript>2</Subscript>, CH<Subscript>3</Subscript>)

The geometries and isomerization of the alkylidene germylenoid H₂C=GeLiF as well as its insertion reactions with R-H (R = F, OH, NH₂, CH₃) have been systematically investigated at the B3LYP/6-311+ G* level of theory. The potential barriers of the four insertion reactions are 110.6, 145.0, 179.4, and 250.6 kJ/mol, respectively. Here, all the mechanisms of the four reactions are identical to each other, i.e., an intermediate has been formed first during the insertion reaction. Then, the intermediate could dissociate into the substituted germylene (H₂C=GeHR) and LiF with a barrier corresponding to their respective dissociation energies. Correspondingly, the reaction energies for the four reactions are 43.6, 78.8, 113.5, and 128.0 kJ/mol, respectively. Compared with the insertion reaction of H₂C= Ge∶ and R-H, the introduction of LiF makes the insertion reaction occur more difficultly. Furthermore, the effects of halogen (F, Cl, Br) substitution and inorganic salts employed on the reaction activity have also been discussed. As a result, the relative reactivity among the four insertion reactions should be as follows: H-F > H-OH > H-NH₂ > H-CH₃.     

Rate constants for hydrogen abstraction reactions of the sulfate radical,SO4−. Alcohols

Rate constants have been determined for the reactions of SO₄^? with a series of alcohols, including hydrated formaldehyde. The SO₄^? radical was produced by the laser-flash photolysis of persulfate, S₂O₈^2?. Rate constants for the reactions of SO₄^? with alcohols range from 1.0 × 10⁷ for methanol to 3.4 × 10⁸ M^?1 s^?1 for 1-octanol. Rate constants for the reactions of SO₄^? with deuterated methanol and ethanol are lower by about a factor of 2.5. For methanol, ethanol, and 2-propanol, the temperature dependence of the rate constant was determined over the range 10–45°C.     

Theoretical study on the insertion reactions of the germylenoid H2GeClMgCl with RH (R = F, OH, NH2)

The insertion reactions of the germylenoid H₂GeClMgCl with RH (R = F, OH, NH₂) have been studied by using the DFT B3LYP and QCISD methods. The geometries of the stationary points on the potential energy surfaces of the reactions were optimized at the B3LYP/6-311+G(d, p) level of theory. The calculated results indicate that all the mechanisms of the three insertion reactions are identical to each other. The QCISD/6-311++G(d, p)//B3LYP/6-311+G(d, p) calculated potential energy barriers for the three insertion reactions of R = F, OH, and NH₂ are 164.62, 193.30, and 200.73 kJ mol^?1, and the reaction energies for the three reactions are ?57.46, ?35.65, and ?22.22 kJ mol^?1, respectively. Under the same situation, the insertion reactions should occur easily in the following order H-F > H-OH > H-NH₂. In THF solvent the insertion reactions get more difficult than in gas phase.     

Ferrite nanoparticles supported on natural wool in one‐pot tandem oxidative reactions: strategy to synthesize benzimidazole,quinazolinone and quinoxaline derivatives

Two tandem oxidative two‐component reactions (O‐2CRs) and Ugi‐type three‐component reactions (OU‐3CRs) of aromatic hydrocarbons of petroleum naphtha have been investigated for the synthesis of 2‐phenyl‐1H ‐benzo [d ]imidazole, 2‐aryl‐4‐quinazolinone and 3,4‐dihydroquinoxalin‐2‐amine derivatives using six new biopolymer‐supported ferrite nanocatalysts: CoFe₂O₄@wool‐SO₃H, MnFe₂O₄@wool‐SO₃H, ZnFe₂O₄@wool‐SO₃H, MnCoFe₂O₄@wool‐SO₃H, ZnCoFe₂O₄@wool‐SO₃H and CrCoFeO₄@wool‐SO₃H. The best results are obtained with the CrCoFeO₄@wool‐SO₃H catalyst. All of the catalysts were characterized using flame atomic absorption spectrometry, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy and energy‐dispersive spectroscopy. To the best of our knowledge, this approach can be considered as the first example of O‐2CRs and OU‐3CRs of aromatic hydrocarbons of petroleum naphtha with ferrite nanocatalysts, which would be very useful from a practical point of view. Copyright © 2016 John Wiley & Sons, Ltd.     

Lithium insertion into titanium dioxide (anatase) electrodes: microstructure and electrolyte effects

Insertion characteristics of anatase electrodes were studied on single-crystal and polycrystalline electrodes of different microstructures. The lithium incorporation from propylene carbonate solution containing LiClO₄ and Li(CF₃SO₂)₂N was studied by means of cyclic voltammetry (CV), the quartz crystal microbalance (QCM) and the galvanostatic intermittent titration technique (GITT). The electrode microstructure affects both the accessible coefficient x and the reversibility of the process. The highest insertion activity was observed for electrodes composed of crystals with characteristic dimensions of ∼10^–8 m. The insertion properties deteriorate for higher as well as for smaller crystal sizes. Enhanced insertion was observed in Li(CF₃SO₂)₂N-containing solutions. Lithium insertion is satisfactorily reversible for mesoscopic electrodes; the reversibility in the case of compact polycrystalline and single-crystal electrodes is poor. The reversibility of the insertion improves with increasing electrolyte concentration. The lithium diffusion coefficient decreases with increasing x and ranges between 10^–15 and 10^–18 cm² s^–1. Electronic Publication     

Molten lithium sulphate-sodium sulphate—potassium sulphate eutectic. The reactions of six vanadium compounds

The solubilities and thermal stability of six vanadium compounds of oxidation states V, IV and III [i.e., V₂O₅, NaVO₄, Na₃VO₄, VOSO₄, VO₂ and KV(SO₄)₂] have been studied in the ternary eutectic (78 mole % Li₂SO₄, 8.5 mole % Na₂SO₄, 13.5 mole % K₂SO₄) and the products of their reactions with basic, acidic, oxidising and reducing reagents have been identified.     

The insertion and H<Subscript>2</Subscript> elimination reactions of H<Subscript>2</Subscript>GeFMgF germylenoid with RH (R = Cl,SH, PH<Subscript>2</Subscript>)

In present paper, the insertion and H₂ elimination reactions of H₂GeFMgF germylenoid with RH (R = Cl, SH, PH₂) were investigated by means of B3LYP and QCISD calculation methods. One transition state and one intermediate were found along the potential energy surface in each insertion reaction, while for the H₂ elimination reactions, only one transition state was found between the reactants and products in each reaction process. Both for the insertion and H₂ elimination reactions, RH reactivity increases in the following order: H–Cl > H–SH > H–PH₂. The insertion and H₂ elimination reactions were compared, and the results demonstrated that the H₂ elimination should be more favorable than the corresponding insertion. The solvent effects on these two types of reactions were considered. The calculated results indicated that the solvents could accelerate the reactions by reducing their barrier heights.     

A novel and efficient solvent-free and heterogeneous method for the synthesis of primary, secondary and bis-N-acylsulfonamides using metal hydrogen sulfate catalysts

Some metal hydrogen sulfates were used as acid catalysts in the N-acylation of different sulfonamides using carboxylic acid chlorides and anhydrides as acylating agents under both heterogeneous and solvent-free conditions. Al(HSO₄)₃ and Zr(HSO₄)₄ were found to have the highest activity and catalyze the reactions efficiently to furnish the primary N-acyl sulfonamides (RCONHSO₂R′), secondary N-acylsulfonamides (RCONR″SO₂R′) and bis-N-acylsulfonamnides [RCO(SO₂R′)N-R″-N(SO₂R′)COR] in good to high yield. The mild reaction conditions, inexpensive and low toxicity of catalysts and easy work-up procedure make this method attractive.