RESUMEN
Increasing environmental problems intensify the demand for high-performance environmental purification materials. MXene is a typical transition-metal carbide/nitride material with a two-dimensional geometric feature and a good deal of functional groups, and it is considered as an efficient adsorbent for removing pollutants from wastewater. However, the easy oxidation and relatively low adsorption capacity greatly restrict its application. In this study, the MXene/polydopamine (PDA) composite particles were fabricated through the biomimetic modification method of inducing the self-polymerization of dopamine in an MXene aqueous solution. Microstructure characterizations demonstrate that PDA facilitates the exfoliation of MXene. Adsorption measurements show that MXene and PDA exhibit an apparent synergistic effect in removing chromium hexavalent Cr(VI) from aqueous solution, and more PDA content leads to a larger synergistic effect. Consequently, the composite particles exhibit an ultrahigh adsorption capacity (862.3 mg/g). Specifically, even if the composite particles were stored in aqueous solution for 2 months, they still exhibit high adsorption ability with only a 3.3% loss in adsorption capacity, indirectly confirming the enhanced stability of MXene induced by PDA. Furthermore, the composite particles also show reduction ability to Cr(VI) and about 54.3% Cr(VI) can be reduced to harmless chromium trivalent Cr(III). This study provides a new method for the preparation of MXene-based adsorbents with excellent adsorption capacity and high stability, which has broad application prospects in the field of wastewater treatment.
RESUMEN
Isocoumarins and dihydroisocoumarins are important skeletons with a wide range of biological activities, such as anti-bacterial, anti-allergy, anti-fungal, anti-tumor, and anti-HIV properties. Herein, we demonstrated divergent syntheses of isocoumarins and 3,4-dihydroisocoumarins by intramolecular dehydrogenative cyclization of 2-(3-oxobutyl) benzoic acids. This transformation undergoes Csp3-H bonds and O-H bonds coupling in air using copper salt. The reactions may undergo free radical process.
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The one-step strategy for the facile syntheses of structurally diverse 1-indanones in moderate to good isolated yields was developed via a ruthenium-catalyzed tandem coupling and cyclization of simple aromatic acids with α,ß-unsaturated ketones. The tandem cyclization involves one-pot sequential reactions of C-H activation, conjugate addition, Dieckmann condensation, Michael addition, intramolecular Aldol reaction, or hydrolysis. Switchable access to spiroindanones and 2-substituted 1-indanones could be achieved by manganese additive and H2O. Mn(II) additive is found to play an important role in this transformation, and a trace amount of water can promote the formation of 2-substituted 1-indanones. This process features the one-pot efficient construction of multiple C-C bonds, high step-economy, commercially available starting materials, and a broad substrate scope.
RESUMEN
A catalyst-free multicomponent CDC reaction is rarely reported, especially for the intermolecular tandem CDC cyclization, which represents an important strategy for constructing cyclic compounds. Herein, a three-component tandem CDC cyclization by a Pummerer-type rearrangement to afford biologically relevant isoindolinones from aromatic acids, amides, and DMSO, is described. This intermolecular tandem reaction undergoes a C(sp(2) )-H/C(sp(3) )-H cross-dehydrogenative coupling, C-N bond formation, and intramolecular amidation. A notable feature of this novel protocol is avoiding a catalyst and additive (apart from oxidant).
RESUMEN
The direct addition of Csp(2) -H bonds onto polar C=C, C=O, and C=N bonds is both synthetically and mechanistically important, because using aromatic C-H substrates in place of organometallic reagents provides a more direct and atom-economical alternative to many important compounds without the pre-generation of organometallic compounds from stoichiometric halides and the unavoidable generation of stoichiometric metal halide waste. In this account, we summarize our contributions to the transition-metal-catalyzed addition of aromatic C-H bonds to polar C=C, C=O, and C=N bonds via directing-group-assisted regiospecific reactions. These synthetic methods provide efficient access to benzylic alcohols, alkylbenzenes, 3-substituted phthalides, N-substituted phthalimides, N-aryl benzamides, and indene derivatives from commercially available reagents. It is worth noting that valuable heterocycles such as 3-substituted phthalides and N-substituted phthalimides can be obtained in one step by this approach.
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The rhodium-catalyzed amidation of substituted benzoic acids with isocyanates by directed CH functionalization followed by decarboxylation to afford the corresponding N-aryl benzamides is demonstrated, in which the carboxylate serves as a unique, removable directing group. Notably, less common meta-substituted N-aryl benzamides are generated readily from more accessible para- or ortho-substituted groups by employing this strategy.
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A rhodium-catalyzed one-pot access to valuable polycyclic frameworks of fluorenone-4-carboxylic acids and diphenic anhydrides via the oxidative dimeric cyclization of aromatic acids has been developed. This transformation proceeded via carboxyl-assisted 2-fold C-H activation followed by intramolecular Friedel-Crafts or dehydration reactions. The silver salt additive plays a vital role in the chemoselectivity of the products. Diphenic anhydride 3l exhibits a maximum fluorescence quantum yield of up to 59%.
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The efficient construction of π-conjugated polycyclic heteroarenes represents a significant task in the field of functional materials. A one-step oxidative tandem cyclization of aromatic acids with (benzo)thiophenes was developed to access planar sulfur-containing polycyclic heteroarenes. This protocol undergoes intermolecular cross-dehydrogenative coupling followed by intramolecular Friedel-Crafts acylation and provides a facile pathway to planar polycyclic compounds from inexpensive reactants. The synthesized heteroarenes serving as lipid-droplet-targeted probes exhibit outstanding performance with favorable biocompatibility and photostability.
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A facile and practical method that the copper powder-catalyzed Ullmann amination of aryl halides with aqueous methylamine under organic solvent- and ligand-free condition at 100 °C and in air gave N-arylamines as sole products in good to excellent yields. The presence of a small amount of air is essential. Other aliphatic primary amines show good to very high reactivity. Secondary amines and aniline are not reactive. Sensitive substituents (i.e., CHO, MeCO, CN and Cl) are tolerable in the reaction.
Asunto(s)
Aminas/química , Cobre/química , Hidrocarburos Halogenados/química , Polvos/química , Solventes/química , Aminación , Catálisis , Estructura MolecularRESUMEN
A very simple, efficient, and regiospecific protocol for aminobromination of a wide scope of beta-nitrostyrene derivatives with N-bromoacetamide (NBA) as nitrogen/bromine sources has been developed by using K(3)PO(4) as catalyst. The reaction proceeded smoothly and cleanly to give the bromoamines in good to excellent yields (78-99%) within 24 h in CH(2)Cl(2) at room temperature without protection of inert gases. A possible mechanism involving a nucleophilic conjugate addition was proposed.
Asunto(s)
Acetamidas/química , Aminas/química , Bromo/química , Fosfatos/química , Compuestos de Potasio/química , Estirenos/química , Catálisis , Cristalografía por Rayos X , Cloruro de Metileno/química , Estructura Molecular , EstereoisomerismoRESUMEN
The aromatic aldehyde as a traceless directing group for the regionselective C-H alkylation catalyzed by rhodium(III) under aerobic atmospheric conditions has been developed. The process involves an aldehyde assisted direct addition of C-H bond to unsaturated electrophiles of acrylates or acrylic acids, and the subsequent decarbonylation. A trace amount of water is found to favor the reaction.
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Controllable rhodium(III)-catalyzed tandem [3+2] cyclization of aromatic aldehydes with maleimides is developed for the divergent synthesis of stereoselective indane-fused pyrrolidine-2,5-dione. Switchable access to different products could be achieved by employing different additives and varying the reaction time. This atom-economic transformation proceeds efficiently via the C-H bond activation directed by weakly coordinating aldehydes and is characterized by exclusive stereoselectivity, air atmosphere, and being free of nitrogen-based transient directing groups.
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An efficient and reusable catalyst with PdEDTA immobilized in an ionic liquid brush and a green procedure have been developed for coupling aryl iodides and bromides with phenylboronic acid. These reactions were conducted in water under aerobic conditions with water-insoluble or even solid aryl halides. The protocol has the advantages of excellent yields, environmental friendliness, and catalyst recyclability. There was no apparent loss of catalyst efficiency until the 10th cycle.
RESUMEN
The regio- and stereoselective aminobromination of alpha,beta-unsaturated ketones catalyzed by copper powder has been established with 4-TsNH(2) and NBS as the nitrogen/bromine sources, respectively. This method provides an easy access for preparation of vicinal aminohalo derivatives in the presence of 1 mol % catalyst. Electron-rich alpha,beta-unsaturated ketones afforded the corresponding aminobrominated products in excellent yields (up to 99.8%), revealing that the addition has an electrophilic feature.
Asunto(s)
Cobre/química , Hidrocarburos Bromados/síntesis química , Cetonas/química , Alquenos/química , Bencenosulfonatos/química , Catálisis , Chalcona/química , Cristalografía por Rayos X , Cetonas/síntesis química , Estereoisomerismo , Sulfonamidas/química , Tolueno/análogos & derivados , Tolueno/químicaRESUMEN
An efficient KI-catalyzed aminobromination of olefins has been developed with good to excellent yields and high regio- and stereoselectivities under transition metal-free conditions. A series of olefins, including alpha,beta-unsaturated carbonyl compounds and simple olefins, was studied. The reaction was performed in CH(2)Cl(2) using KI as the catalyst and TsNH(2) and NBS as the nitrogen and bromine sources.
Asunto(s)
Alquenos/química , Bromo/química , Silicio/química , Catálisis , Técnicas Químicas Combinatorias , HalogenaciónRESUMEN
In the title compound, C(23)H(26)O(4), there is a dihedral angle of 83.7â (6)° between the two benzene rings. The five-membered rings have chair conformations.
RESUMEN
A novel rhodium(III)-catalyzed direct functionalization of the ortho-C-H bond of aromatic ketone derivatives and an intramolecular cyclization sequence produced indene derivatives in moderate to good yields. This cascade cyclization involves a conjugate addition of α,ß-unsaturated ketone and subsequent aldol condensation. The reaction occurred efficiently in the presence of water and under an atmosphere of air.
Asunto(s)
Indenos/síntesis química , Cetonas/química , Cetonas/síntesis química , Rodio/química , Alquenos/química , Catálisis , Ciclización , Indenos/química , Estructura Molecular , Estereoisomerismo , Agua/químicaRESUMEN
Silicon powder was found, for the first time, to be an efficient alternative to transition metal catalysts for aminobromination of alpha,beta-unsaturated carbonyl compounds and simple olefins with p-toluenesulfonamide (4-TsNH(2)) and NBS, affording the aminobrominated products in high yields and regio- and stereoselectivity. The high reactivity of electron-rich substrates reveals that the reaction has the electrophilic addition feature.