Ligand Promoted Pd-Catalyzed High para-Selective C-H Olefination.

Achieving high para-selective C-H functionalized products of benzoic acid derivatives using a designed template is still a daunting challenge because the carbonyl group also could coordinate with metal to activate the ortho-C-H bond. Herein, we report the ligand promoted high para-selective C-H olefination of benzoic acid derivatives; we screened a series of ligands increasing the ratio of p:others from 62:38 to 96:4. This work may find application in the construction of para-substituted benzoic acid derivatives.

A Cheap and Efficient Oxidant (n-Bu)4NNO3-Enabled C(sp2)- and C(sp3)-H Olefination at Room Temperature.

To further promote the widely practical application of C-H activation, developing green and mild reaction conditions has invariably been the objective of researchers, especially when it comes to remote C-H activation reactions. Herein, we report a new cheap and powerful (n-Bu)4NNO3 oxidant. This oxidant is efficient and universal for Pd(II)-catalyzed sp2 and sp3 C-H olefination and allows the reaction to be carried out at room temperature. Because of this, we attempted to make C-H functionalization more economical and environmentally benign.

Selective and Efficient Synthesis of Pine Sterol Esters Catalyzed by Deep Eutectic Solvent.

Phytosterol esters have attracted widespread academic and industrial interests due to their advantages in lowering cholesterol, as antioxidants, and in preventing or treating cancer. However, the generation of by-products limits the application of phytosterol esters in food fields. In this study, deep eutectic solvents (DESs), a series of green, nontoxic, low-cost and biodegradable solvents, were adopted as the catalyst for the synthesis of pine sterol esters. The results showed that the acidic DES which was prepared with choline chloride (ChCl) and p-toluene sulfonic acid monohydrate (PTSA) with a molar ratio of 1:3 performed best in the prescreening experiments. To further improve the efficiency of the pine sterol ester, the molar ratio of substrates, the amount of catalyst, the reaction temperature and the reaction time were optimized, and its yield was improved to 94.1%. Moreover, the by-products of the dehydration side reactions of the sterol can be efficiently inhibited. To make this strategy more universal, other fatty acids were also used as the substrate for the synthesis of pine sterol esters, and a yield of above 92.0% was obtained. In addition, the reusability of DES was also investigated in this study, and the efficiency of DES was well maintained within five recycled uses. Finally, DFT calculations suggested that the suitable H-bonds between ChCl and PTSA decreased the nucleophilic capacity and increased the steric hindrance of the latter, and further prevented the attack on ßH and reduced the generation of by-products. This study developed a reliable and eco-friendly strategy for the preparation of high-quality phytosterol esters with low-dosage catalyst usage and high selectivity.

Cobalt(III)-catalyzed weakly coordinating arylurea-directed regioselective mono-olefination.

Here, we developed an air-stable, earth-abundant cobalt(III)-catalyzed regioselective mono-olefination of arenes directed by urea under mild conditions through a cross-dehydrogenative coupling (CDC) process. Under the optimized conditions, a high regioselectivity of mono-olefination was achieved with various electron-rich and electron-deficient arenes, which afforded E-alkenylated products (with yields of up to 90%). In contrast to the conditions used for noble-metal-catalyzed olefination directed by weakly coordinating groups, our reaction was operated under mild conditions, including mild temperature (40 °C) and non-metallic oxidant.

Magnetic Polyethyleneimine Nanoparticles Fabricated via Ionic Liquid as Bridging Agents for Laccase Immobilization and Its Application in Phenolic Pollutants Removal.

In this study, polyethyleneimine was combined with magnetic Fe3O4 nanoparticles through the bridging of carboxyl-functionalized ionic liquid, and laccase was loaded onto the carrier by Cu2+ chelation to achieve laccase immobilization (MCIL-PEI-Cu-lac). The carrier was characterized by Fourier transform infrared spectroscopy, scanning electron microscope, thermogravimetric analysis, X-ray diffraction analysis, magnetic hysteresis loop and so on. MCIL-PEI-Cu-lac has good immobilization ability; its loading and activity retention could reach 52.19 mg/g and 91.65%, respectively. Compared with free laccase, its thermal stability and storage stability have been significantly improved, as well. After 6 h of storage at 60 °C, 51.45% of the laccase activity could still be retained, and 81.13% of the laccase activity remained after 1 month of storage at 3 °C. In the pollutants removal test, the removal rate of 2,4-dichlorophenol (10 mg/L) by MCIL-PEI-Cu-lac could reach 100% within 10 h, and the removal efficiency could still be maintained 60.21% after repeated use for 8 times. In addition, MCIL-PEI-Cu-lac also has a good removal effect on other phenolic pollutants (such as bisphenol A, phenol, 4-chlorophenol, etc.). Research results indicated that an efficient strategy for laccase immobilization to biodegrade phenolic pollutants was developed.

Co-immobilization of electron mediator and laccase onto dialdehyde starch cross-linked magnetic chitosan nanomaterials for organic pollutants' removal.

In this study, an amino-functionalized ionic liquid-modified magnetic chitosan (MACS-NIL) containing 2,2-diamine-di-3-ethylbenzothiazolin-6-sulfonic acid (ABTS) was used as a carrier, and dialdehyde starch (DAS) was used as a cross-linking agent to covalently immobilize laccase (MACS-NIL-DAS-lac), which realized the co-immobilization of laccase and ABTS. The carrier was characterized by Fourier infrared transform spectroscopy, scanning electron microscopy, thermogravimetric analysis, X-ray diffraction analysis, electron paramagnetic resonance, etc. The immobilization efficiency and activity retention of MACS-NIL-DAS-lac could reach 76.7% and 69.8%, respectively. At the same time, its pH stability, thermal stability, and storage stability had been significantly improved. In the organic pollutant removal performance test, the removal rate of 2,4-dichlorophenol (10 mg/L) by MACS-NIL-DAS-lac (1 U) could reach 100% within 6 h, and the removal efficiency could still reach 88.6% after six catalytic runs. In addition, MACS-NIL-DAS-lac also showed excellent degradation ability for other conventional phenolic pollutants and polycyclic aromatic hydrocarbons. The research results showed that MACS-NIL-DAS fabricated by the combination inorganic material, organic biomacromolecules, ionic liquid, and electron mediator could be used as a novel carrier for laccase immobilization and the immobilized laccase showed excellent removal efficiency for organic pollutants.

Immobilization of Interfacial Activated Candida rugosa Lipase Onto Magnetic Chitosan Using Dialdehyde Cellulose as Cross-Linking Agent.

Candida rugosa lipase (CRL) was activated with surfactants (sodium dodecyl sulfate [SDS]) and covalently immobilized onto a nanocomposite (Fe3O4-CS-DAC) fabricated by combining magnetic nanoparticles Fe3O4 with chitosan (CS) using polysaccharide macromolecule dialdehyde cellulose (DAC) as the cross-linking agent. Fourier transform infrared spectroscopy, transmission electron microscope, thermogravimetric analysis, and X-ray diffraction characterizations confirmed that the organic-inorganic nanocomposite support modified by DAC was successfully prepared. Enzymology experiments confirmed that high enzyme loading (60.9 mg/g) and 1.7 times specific enzyme activity could be obtained under the optimal immobilization conditions. The stability and reusability of immobilized CRL (Fe3O4-CS-DAC-SDS-CRL) were significantly improved simultaneously. Circular dichroism analysis revealed that the active conformation of immobilized CRL was maintained well. Results demonstrated that the inorganic-organic nanocomposite modified by carbohydrate polymer derivatives could be used as an ideal support for enzyme immobilization.

Enhancing the Catalytic Performance of Candida antarctica Lipase B by Chemical Modification With Alkylated Betaine Ionic Liquids.

Various betaine ionic liquids composed of different chain lengths and different anions were designed and synthesized to modify Candida antarctica lipase B (CALB). The results showed that the catalytic activity of all modified lipases improved under different temperature and pH conditions, while also exhibiting enhanced thermostability and tolerance to organic solvents. With an increase in ionic liquid chain length, the modification effect was greater. Overall, CALB modified by [BetaineC16][H2PO4] performed best, with the modified CALB enzyme activity increased 3-fold, thermal stability increased 1.5-fold when stored at 70°C for 30 min, with tolerance increased 2.9-fold in 50% DMSO and 2.3-fold in 30% mercaptoethanol. Fluorescence and circular dichroism (CD) spectroscopic analysis showed that the introduction of an ionic liquid caused changes in the microenvironment surrounding some fluorescent groups and the secondary structure of the CALB enzyme protein. In order to establish the enzyme activity and stability change mechanisms of the modified CALB, the structures of CALB modified with [BetaineC4][Cl] and [BetaineC16][Cl] were constructed, while the reaction mechanisms were studied by molecular dynamics simulations. Results showed that the root mean square deviation (RMSD) and total energy of modified CALB were less than those of native CALB, indicating that modified CALB has a more stable structure. Root mean square fluctuation (RMSF) calculations showed that the rigidity of modified CALB was enhanced. Solvent accessibility area (SASA) calculations exhibited that both the hydrophilicity and hydrophobicity of the modified enzyme-proteins were improved. The increase in radial distribution function (RDF) of water molecules confirmed that the number of water molecules around the active sites also increased. Therefore, modified CALB has enhanced structural stability and higher hydrolytic activity.

Chemical modification for improving catalytic performance of lipase B from Candida antarctica with hydrophobic proline ionic liquid.

In this study, a series of proline ionic liquids with different lengths of hydrophobic alkyl on the side chain were used to modify the Candida Antarctic lipase B (CALB). The catalytic activity, thermal stability and tolerance to methanol and DMSO of the modified enzyme were all improved simultaneously. The optimum temperature changed from 55 to 60 â„ƒ. The hydrophobicity and anion type of the modifier have important influence on the catalytic performance of CALB. CALB modified by [ProC12][H2PO4] has a better effect. Under the optimal conditions, its hydrolysis activity was 3.0 times than that of the native enzyme, the catalytic efficiency Kcat/Km improved 2.8 times in aqueous phase, and the tolerance to organic solvent with strong polarity (50% methanol 2 h) was increased by 6.8 times. Fluorescence spectra and circular dichroism (CD) spectroscopy showed that the introduction of ionic liquids changed the microenvironment near the fluorophores of the enzyme protein, the α-helix decreased and ß-sheet increased in the secondary structure of the modified enzymes. The root mean square deviation (RMSD), residue root mean square fluctuation (RMSF), radius of gyration (Rg), and solution accessible surface area (SASA) of [ProC2][Br]-CALB, [ProC12][Br]-CALB and native CALB were obtained for comparison by molecular dynamics simulation. The results of dynamics simulation were in good agreement with enzymology experiment. The introduction of ionic liquids can keep CALB in a better active conformation, and proline ionic liquids with long hydrophobic chains can significantly improve the surface hydrophobicity and overall rigidity of CALB. This research offers a new idea for rapid screening of efficient modifiers and provision of enzymes with high stability and activity for industrial application.

Co-immobilization of laccase and ABTS onto amino-functionalized ionic liquid-modified magnetic chitosan nanoparticles for pollutants removal.

This work aims to achieve the co-immobilization of laccase and 2,2-binamine-di-3-ethylbenzothiazolin-6-sulfonic acid (ABTS) to improve removal capability of the biocatalyst for pollutants while avoiding potential pollution caused by ABTS. The laccase was immobilized on magnetic chitosan nanoparticles modified with amino-functionalized ionic liquid containing ABTS (MACS-NIL) based on Cu ion chelation (MACS-NIL-Cu-lac). The carrier was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, x-ray diffraction and etc., and electron paramagnetic resonance confirmed the mediator molecule ABTS on the carrier could also play the role of electron transmission. MACS-NIL-Cu-lac presented relatively high immobilization capacity, enhanced activity (1.7-fold that of free laccase), improved pH and temperature adaptability, and increased thermal and storage stability. The removal performance assay found that MACS-NIL-Cu-lac had a good removal efficiency with 100.0 % for 2,4-dichlorophenol in water at 25 °C, even when the concentration reached 50 mg/L. Reusability study showed that after six catalytic runs, the removal efficiency of 2,4-dichlorophenol by MACS-NIL-Cu-lac could still reach 93.2 %. Additionally, MACS-NIL-Cu-lac exhibited higher catalytic efficiencies with 100.0 %, 70.5 % and 93.3 % for bisphenol A, indole, and anthracene, respectively. The high catalytic performance in pure water system obtained by the novel biocatalyst co-immobilizing laccase and electron mediator ABTS showed greater practical application value.

Rh(III)-Catalyzed C(sp3)-H Acetoxylation of 8-Methylquinolines.

A mild and efficient Rh(III)-catalyzed aliphatic C-H acetoxylation directed by quinolines has been developed with widespread functional groups, including various halogens, which usually can provide precursors for further organic synthesis but easily results in selectivity issues in the Pd- and Ni-catalyzed reaction. Interestingly, Ac2O plays an essential role in promoting the transformation.

One-pot cascade synthesis of benzopyrans and dihydropyrano[c]chromenes catalyzed by lipase TLIM.

Lipase TLIM was reported to be an efficient, commercially available and reusable catalyst for the Knoevenagel-Michael cascade reactions of aldehydes, malononitrile/ethyl cyanoacetate and 4-hydroxycoumarin/1, 3-cyclohexanedione/dimedone in aqueous DMSO. This methodology presents many superiorities such as simple procedure, mild reaction conditions, commercially available and reusable catalyst, high substrate applicability, the ability to be scaled up, and good to excellent yields.

Enzymatic approach to cascade synthesis of bis(indolyl)methanes in pure water.

A mild, efficient, and green protocol was developed for the synthesis of bis(indolyl)methanes catalyzed by lipase TLIM through the cascade reactions of indole with aldehydes in pure water. This methodology offers many superiorities such as excellent yields, wide substrate range, simple procedure, reusable and minimal amount of catalyst, and the ability to be scaled up.

Synthesis of hyaluronic acid hydrogels by crosslinking the mixture of high-molecular-weight hyaluronic acid and low-molecular-weight hyaluronic acid with 1,4-butanediol diglycidyl ether.

High molecular weight hyaluronic acid (HMW-HA) and low molecular weight hyaluronic acid (LMW-HA) were mixed at different ratios and cross-linked with 1,4-butanediol diglycidyl ether (BDDE) to prepare five hyaluronic acid hydrogels A-E. Enzymolysis stability, swelling rate, crosslinking degree, rheological characteristics, BDDE residual rate, surface microstructure, and cytotoxicity of different hydrogels were investigated. The results showed that hydrogel B obtained by 10% HA (w/v, HMW-HA and LMW-HA having a mass ratio of 4 : 1) crosslinking with 1% BDDE (v/v) had stronger in vitro anti-degradation ability, better mechanical properties and lower cytotoxicity than those prepared by mixing in different proportions. Hydrogel B has potential applications in regenerative medicine and tissue engineering.

Ligand-Promoted RhIII -Catalyzed Thiolation of Benzamides with a Broad Disulfide Scope.

A ligand-promoted RhIII -catalyzed C(sp2 )-H activation/thiolation of benzamides has been developed. Using bidentate mono-N-protected amino acid ligands led to the first example of RhIII -catalyzed aryl thiolation reactions directed by weakly coordinating directing amide groups. The reaction tolerates a broad range of amides and disulfide reagents.

Rh(III)-Catalyzed meta-C-H Alkenylation with Alkynes.

Rh(III)-catalyzed meta-C-H functionalization reactions are still rare. Herein, we report the first example of Rh(III)-catalyzed meta-C-H alkenylation with disubstituted alkynes directed by a U-shaped nitrile template. Exclusive regio-selectivity has been achieved using unsymmetrical aryl and alkyl-disubstituted alkynes to afford synthetically valuable trisubstituted olefins. Propargyl alcohols are also compatible, affording complex allylic alcohols. Notably, transition metal-catalyzed meta-alkenylation with alkynes has not been successful with Pd catalysts.

Porous Metal-Organic Frameworks with Chelating Multiamine Sites for Selective Adsorption and Chemical Conversion of Carbon Dioxide.

A combination of carbon dioxide (CO2) capture and chemical fixation in a one-step process is attractive for chemists and environmentalists. In this work, by incorporating chelating multiamine sites to enhance the binding affinity toward CO2, two novel metal-organic frameworks (MOFs) [Zn2(L)(2,6-NDC)2(H2O)]·1.5DMF·2H2O (1) and [Cd2(L)(2,6-NDC)2]·1.5DMF·2H2O (2) (L = N1-(4-(1 H-1,2,4-triazole-1-yl)benzyl)- N1-(2-aminoethyl)ethane-1,2-diamine, 2,6-H2NDC = 2,6-naphthalenedicarboxylic acid, DMF = N, N-dimethylformamide) were achieved under solvothermal conditions. Both 1 and 2 possess high selectivity for adsorption of CO2 over CH4 at room temperature under atmospheric pressure. Moreover, 1 has one-dimensional tubular channels decorated with multiactive sites including NH2 groups and coordination unsaturated Lewis acid metal sites, leading to efficient catalytic activity for chemical fixation of CO2 by reaction with epoxides to give cyclic carbonates under mild conditions.

Rhodium-Catalyzed Direct Ortho C-H Arylation Using Ketone as Directing Group with Boron Reagent.

A general method for selective ortho C-H arylation of ketone, with boron reagent enabled by rhodium complexes with excellent yields, is developed. The transformation is characterized by the use of air-stable Rh catalyst, high monoarylation selectivity, and excellent yields of most of the substrates.

Ligand-Promoted Rhodium(III)-Catalyzed ortho-C-H Amination with Free Amines.

Ligand development for rhodium(III)-catalyzed C-H activation reactions has largely been limited to cyclopentadienyl (Cp) based scaffolds. 2-Methylquinoline has now been identified as a feasible ligand that can coordinate to the metal center of Cp*RhCl to accelerate the cleavage of the C-H bond of N-pentafluorophenylbenzamides, providing a new structural lead for ligand design. The compatibility of this reaction with secondary free amines and anilines also overcomes the limitations of palladium(II)-catalyzed C-H amination reactions.

Rh(III)-Catalyzed meta-C-H Olefination Directed by a Nitrile Template.

A range of Rh(III)-catalyzed ortho-C-H functionalizations have been developed; however, extension of this reactivity to remote C-H functionalizations through large-ring rhodacyclic intermediates has yet to be demonstrated. Herein we report the first example of the use of a U-shaped nitrile template to direct Rh(III)-catalyzed remote meta-C-H activation via a postulated 12-membered macrocyclic intermediate. Because the ligands used for Rh(III) catalysts are significantly different from those of Pd(II) catalysts, this offers new opportunities for future development of ligand-promoted meta-C-H activation reactions.