Exploring the Performance Improvement for CO2 Chemical Fixation in Zn/ZnMg-MOFs.

A new 3D zinc-based metal-organic framework {[Zn7L2(DMF)3(H2O)(OH)2]·5DMF}n (1) (H6L = 5,5',5″-(methylsilanetriyl) triisophthalic acid) was constructed with an organosilicon-based linker, where H6L is a tetrahedral structure furnished with rich -COO- chelating sites for Zn(II) immobilization. Compound 1 exhibited two types of irregular one-dimensional channels and a three-dimensional skeleton with large specific surface area, making it a promising catalytic platform. Moreover, by incorporation of the second metal ion into the inorganic node of framework 1, isomorphic bimetallic MOF ZnMg-1 was successfully synthesized. ZnMg-1 demonstrated enhanced catalytic activity compared to 1 under identical conditions. Contrast experiments and theoretical calculations indicate that bimetallic active sites play a facilitating role in the chemical fixation of epoxides and CO2. It indicated that efficient chemical fixation of CO2 to cyclic carbonates was obtained over isomorphic MOF catalysts 1 and ZnMg-1.

Imidazole-Functionalized Polyoxometalate Catalysts for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran Using Atmospheric O2.

Biomass as a sustainable and abundant carbon source has attracted considerable attention as a potential alternative to petroleum resources. The selective oxidation of 5-hydroxymethylfurfural (HMF), a versatile platform molecule, to value-added 2,5-diformylfuran (DFF) provides an efficient pathway for biomass valorization. Herein, three discrete imidazole-functionalized polyoxometalates (POMs), HPMo8VVI4O40(VVO)2[(VIVO)(IM)4]2·nH2O·(IM)m (IM = 1-methylimidazole, n = 4, m = 8 for 1; IM = 1-ethylimidazole, n = 4, m = 9 for 2; IM = 1-propylimidazole, n = 0, m = 4 for 3), have been successfully synthesized by a facile solvothermal method and thoroughly characterized by routine techniques. Compounds 1-3 contain a bi-capped pseudo-Keggin {HPMo8V4O40(VO)2} and two imidazole-functionalized {(VO)(IM)4} groups, which, to our knowledge, represent the first examples of organic-functionalized Mo-V clusters. Compounds 1-3 as heterogeneous catalysts can effectively promote the transformation of HMF to DFF using atmospheric O2 as oxidant. Under minimally optimized conditions, 95% of HMF was converted by 1 with 95% selectivity for DFF and its catalytic activity was basically maintained after five cycles. Moreover, the important roles of the bi-capped pseudo-Keggin cluster and the functionalized V groups in the selective oxidation of HMF have been explored. According to experimental and spectroscopic results, a three-step oxidation mechanism of HMF to DFF has been proposed.

Selective Oxidation of Benzylic C-H Bonds Catalyzed by Cu(II)/{PMo12}.

Precise catalytic regulation of carbon radical generation by a highly active oxygen radical to abstract the H atom in a C-H bond is an effective method for the selective activation of C-H synthetic chemistry. Herein, we report a facile catalyst system with commercially available copper(II)/{PMo12} to form a tert-butanol radical intermediate for the selective oxidation of benzylic C-H bonds. The reaction shows a broad range of substrates (benzyl methylene, benzyl alcohols) with good functional group tolerance and chemical selectivity. The corresponding carbonyl compounds were synthesized with good yields under mild conditions. DFT calculations and experimental analysis further demonstrated a reasonable carbon radical mechanism for this type of organic transformation reaction.

Synthesis of protected α-amino acids via decarboxylation amination from malonate derivatives.

A general and efficient strategy for the synthesis of protected α-amino acids is reported. The method uses malonate derivatives as the starting materials and Cs2CO3 as a base at 60 degrees, giving α-amino acid derivatives in moderate yields by releasing CO2. This methodology shows broad substrate scope (primary and secondary acids), excellent functional group tolerance and high efficiency to give the desired products under mild reaction conditions. It also allows the construction of ß and γ-amino acids and other unnatural products.

pH-Zone-refining counter-current chromatography for two new lipo-alkaloids separated from refined alkaline extraction of Kusnezoff monkshood root.

An efficient and refined method for the separation of six aconitine-type alkaloids from the alkaline prepared "Kusnezoff monkshood root" was established. It is the first study that two new lipo-alkaloids were successfully isolated from refined sample by pH-zone-refining counter-current chromatography rather than synthetic method. It was of interest that a great deal of lipo-alkaloids was produced in crude extract from the alkalization of "Kusnezoff monkshood root." A refined sample method was proposed to enrich two types of alkaloids by liquid-liquid extraction, i.e. lipo-alkaloids and monoester-diterpenoid alkaloids. The pH-zone-refining counter-current chromatography was performed with an optimized two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (3:5:4:5, v/v), where upper organic phase was added to 3 mmol/L triethylamine as a retainer and lower aqueous mobile phase was added to 3 mmol/L hydrochloric acid as an eluter. As a result, six aconitum alkaloids, including two lipo-alkaloids (8-lino-14-benzoylaconine, 8-pal-14-benzoylaconine), three monoester-diterpenoid alkaloids (14-benzoylmesaconine, 14-benzoylaconine, beyzoyldeoxyaconine), and one aconine alkaloid (neoline) were acquired from the plant at the same time. The anti-inflammatory activities of the two new lipo-alkaloids were compared to the six alkaloids in vitro, in cyclo-oxygen-ase-2 inhibition assays. The separation mechanism of six alkaloids by pH-zone-refining counter-current chromatography was illustrated.

Base-Mediated Intramolecular Decarboxylative Synthesis of Alkylamines from Alkanoyloxycarbamates.

A general and effective method for the synthesis of alkylamine via intramolecular decarboxylation of alkanoyloxycarbamates is described. The alkanoyloxycarbamates are readily prepared with alkyl carboxylic acids and hydroxylamine. The reaction shows a broad range of substrates (primary and secondary alkyl) with functional tolerance, and the corresponding products were obtained in good yields under mild conditions.

Synthesis of indoles from aroyloxycarbamates with alkynes via decarboxylation/cyclization.

An efficient Pd-catalyzed decarboxylation/cyclization of aroyloxycarbamates to realize substituted indoles has been disclosed. Terminal alkynes as the coupling partners lead to site specific 2-substituted indoles through two pathways, while internal alkynes with aroyloxycarbamates can be transformed to 2,3-disubstituted indoles directly. This protocol is further demonstrated by the efficient synthesis of indoles as well as the success of employing inexpensive aryl acids as starting materials to construct C-N bonds by releasing CO2.

Regioselective Synthesis of 2-Vinylanilines Using O-aroyloxycarba-mates by Sequential Decarboxylation/Amination/Heck Reaction.

A new sequential approach for 2-vinylanilines utilizing aryl carboxylic acids as stable, inexpensive and widely available arylating reagents is described. Employing a Pd-POVs catalyst system, this protocol is not only overcoming the restriction barrier of decarboxylative coupling to ortho-substituted substrates, but also provides site-special to create new C(sp2)-N and C(sp2)-C(sp2) bonds. Mechanistic experiments suggest the cleavage of C(sp2)-COOH gives priority to C(sp2)-X bond in this reaction.

Unsupported nanoporous gold catalyst for highly selective hydroamination of alkynes.

An efficient and highly selective heterogeneous catalyst system for hydroamination of alkynes was developed using unsupported gold nanopores (AuNPore) for the first time. The AuNPore-catalyzed highly regioselective hydroamination of alkynes proceeded smoothly without any additive and solvent under mild conditions (rt-50 °C) to yield Markovnikov imines in satisfactory to excellent yields. No gold leached from AuNPore during the hydroamination of alkynes. Moreover, the catalyst was easily recovered and reused without any loss of catalytic activity. A one-pot, two-step procedure using a single AuNPore catalyst has been devised to produce secondary amines derived from readily available alkynes and anilines with high atom efficiency.

Copper(ii)-containing tungstotellurates(vi): syntheses, structures and their catalytic performances in selective oxidation of thioethers.

We report the syntheses and structures of two new copper(ii)-containing tungstotellurates(vi) Na12[TeVI 2W8O38Cu2(H2O)2]·7H2O (Te2W8Cu2) and Na6[TeVIW6O24Cu(NH2CH2CO2)2]·6H2O (TeW6Cu). The two compounds were synthesized by a simple one-pot method and characterized by single-crystal X-ray diffraction (XRD), powder XRD, FT-IR spectroscopy, elemental analysis, and thermogravimetric analysis in the solid state. Furthermore, their catalytic properties for the selective oxidation of thioethers were also studied systematically. The catalytic experiment results indicate that the tungstotellurate(vi) Te2W8Cu2 is an effective heterogeneous catalyst for the selective oxidation of thioethers to sulfoxides or sulfones by an H2O2 oxidant at room temperature. Under the ambient conditions, Te2W8Cu2 can convert 99% of methyl(phenyl)sulfane to sulfoxides or sulfones with 96% or 99% selectivity, respectively, and the utilization rate of H2O2 is up to 80%. Furthermore, Te2W8Cu2 as a heterogeneous catalyst is stable in the reaction and could be reused at least five cycles with conserved activity.

Enhancing Methane Aromatization Performance by Reducing the Particle Size of Molybdenum Oxide.

Efficient use of natural gas to produce aromatics is an attractive subject; the process requires catalysts that possess high-performance active sites to activate stable C-H bonds. Here, we report a facile synthetic strategy to modify HMCM-49 with small molybdenum oxide nanoparticles. Due to the higher sublimability of nano-MoO3 particles than commercial MoO3, they more easily enter into the channels of HMCM-49 and associate with Brønsted acid sites to form active MoCx-type species under calcination and reaction conditions. Compared with commercial MoO3 modified MCM-49, nano-MoO3 modified MCM-49 exhibits higher methane conversion (13.2%), higher aromatics yield (9.1%), and better stability for the methane aromatization reaction.

Heterogeneous photocatalytic anaerobic oxidation of alcohols to ketones by Pt-mediated hole oxidation.

We report a platinum nanocluster/graphitic carbon nitride (Pt/g-C3N4) composite solid catalyst with a photocatalytic anaerobic oxidation function for highly active and selective transformation of alcohols to ketones. The desirable products were successfully obtained in good to excellent yields from various functionalized alcohols at room temperature, including unactivated alcohols. Mechanistic studies indicated that the reaction could proceed through a Pt-mediated hole oxidation initiating an α-alcohol radical intermediate followed by a two-electron oxidation pathway. The merit of this strategy offers a general approach towards green and sustainable organic synthetic chemistry.

Electro-synthesized Co(OH)2@CoSe with Co-OH active sites for overall water splitting electrocatalysis.

Constructing noble metal-free electrocatalytically active sites for the simultaneous hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution is key to realizing electricity-driven water splitting in practical applications. Here, we rationally designed Co(OH)2@CoSe nanorods (NRs) as an excellent bifunctional electrocatalyst by an in situ electrochemical transformation strategy, where the Co-based nanorod template was converted into Co(OH)2@CoSe at the cathode. The obtained electrode exhibits superior electrocatalytic activity for both the HER (overpotential of 208 mV at 20 mA cm-2) and the OER (268 mV at 20 mA cm-2) at high current density in a 1 M KOH solution. The theoretical calculations and experimental evidence indicate that the chemical coupling Co-OH active site between Co(OH)2 and CoSe regulates the hydrogen adsorption and desorption energy and fast electron transfer capability, which is responsible for the improved HER. Moreover, the Co(OH)2@CoSe NRs can be further converted into CoOOH nanosheets which serve as OER active sites. Toward practical electrolytic cell applications, the Co(OH)2@CoSe nanorods as both the cathode and anode achieved a current density of 100 mA cm-2 at 1.94 V for overall water splitting, better than that of noble metal-based electrocatalysts.

Cu(i)/{Nb6O19} catalyzed N-acylation of arylacetic acids with amines under aerobic conditions.

The method described herein is a general, efficient and green approach to synthesize α-ketoamides from arylacetic acids and amines. Employing a simple copper(i)/{Nb6O19} catalyst system, the reaction offers a facile process to give functionalized α-ketoamides from readily available arylacetic acids under aerobic conditions. The merit of this new strategy is that it expands the syntheses of α-ketoamides from stable, inexpensive and widely available acylation reagents such as arylacetic acids in one step.

Palladium-Catalyzed Decarboxylative Synthesis of Arylamines.

A novel approach has been developed for the synthesis of arylamines via the palladium-catalyzed intramolecular decarboxylative coupling (IDC) of aroyloxycarbamates, obtained in situ by reacting aryl carboxylic acids with hydroxycarbamates. The reaction offers facile access to structurally diverse arylamines with the site-specific formation of the C(sp2)-N bond under mild conditions.