Ultrastrong and Hydrophobic Sandwich-Structured MXene-Based Composite Films for High-Efficiency Electromagnetic Interference Shielding.

Electromagnetic interference (EMI) shielding materials are highly necessary to solve the problem of electromagnetic radiation. Transition-metal carbide/nitride (MXene) materials offer great potential for the construction of high-performance EMI shields because of their high electrical conductivity and versatile surface chemistry. However, MXene generally suffers from poor mechanical and oxidation-resistant properties, which hinders its practical applications. Herein, flexible, strong, and hydrophobic sandwich-structured composite films (H-S-MXene), consisting of a conductive MXene layer and supporting aramid nanofiber layer, were fabricated using step-by-step vacuum-assisted filtration and dip coating. Given the unique sandwich structure, hydrogen bonding interactions, and covalent cross-linking of the MXene sheets, the H-S-MXene composite films demonstrated simultaneously excellent EMI shielding and mechanical properties. The EMI shielding effectiveness of the H-S-MXene composite film with 20 wt % MXene content reached 46.1 dB at thickness of 23.2 ± 0.5 µm, and the tensile strength of the film reached 302.1 MPa, which outperformed other reported EMI shielding materials. The excellent mechanical flexibility and hydrophobicity of the H-S-MXene composite films ensured a stable EMI shielding performance, which could withstand cycled bending, torsion, and exposure to aqueous environments. These impressive features made the H-S-MXene composite films promising candidates for electronic devices and aerospace. This study provides important guidance for the rational design of stable MXene-based composites with advanced properties.

Tf2O-Mediated Cyclization of α-Acyl-ß-(2-aminopyridinyl)acrylamides: Access to N-Substituted 4H-Pyrido[1,2-a]pyrimidin-4-imines.

A facile and efficient direct synthesis of N-substituted 4H-pyrido[1,2-a]pyrimidin-4-imines is developed from α-acyl-ß-(2-aminopyridinyl)acrylamides mediated by triflic anhydride (Tf2O) in the presence of 2-chloropyridine. This amide activation protocol features mild reaction conditions, simple execution, excellent yields, and high chemoselectivity, and is also applied to the synthesis of substituted 4H-pyrido[1,2-a]pyrimidin-4-ones via a practical one-pot procedure.

Lewis Pair-Mediated Surface-Initiated Polymerization.

We present the first example of surface-initiated polymerization mediated by Lewis pairs for the synthesis of polymer brushes on planar substrates. The method enables the rapid grafting polymerization from the self-assembled monolayer or surface-attached macroinitiators, furnishing linear polymer brushes and bottle-brush brushes. Both homopolyester and block copolyester brushes can be synthesized via this versatile approach. This work not only opens up new opportunities for the application of Lewis pair-mediated polymerization but also enriches the surface-initiated polymerization on different surfaces.

Formal [4 + 1] Annulation of α-Arylhydrazonoketones and Dimethylsulfoxonium Methylide: One-pot Synthesis of Substituted Pyrazoles and Dihydropyrazoles.

A formal [4 + 1] annulation of readily available α-arylhydrazonoketones and trimethylsulfoxonium iodide in the presence of cesium carbonate is described involving a sequential Corey-Chaykovsky reaction and intramolecular nucleophilic cyclization process. Substituted pyrazoles were obtained exclusively from the reactions of α-arylhydrazono-ß-oxo-amides and trimethylsulfoxonium iodide in moderate to good yields, whereas the reactions of α-arylhydrazono-ß-oxo-ketone/α-arylhydrazono- ß-oxo-ester afforded the corresponding dihydropyrazoles in good yields.

POCl3-mediated reaction of 1-acyl-1-carbamoyl oximes: a new entry to cyanoformamides.

A facile and efficient one-pot synthesis of cyanoformamides was developed from readily available 1-acyl-1-carbamoyl oximes mediated by phosphoryltrichloride (POCl3) under mild conditions in good to high yields.

Formal [4+2] annulation of enaminones and cyanomethyl sulfur ylide: one-pot access to polysubstituted pyridin-2(1H)-ones.

A facile and efficient one-pot synthesis of polysubstituted pyridin-2(1H)-ones from readily available enaminones and the cyanomethyl sulfonium bromide salt in the presence of cesium carbonate is developed, and a mechanism involving sequential nucleophilic vinylic substitution (S(N)V), intramolecular nucleophilic cyclization and dealkylation reactions is proposed.

Divergent synthesis of 2,3-dihydro-1H-pyrroles, 3-alkyl-1H-pyrroles and 3-alkenyl-1H-pyrroles from 2,4-pentadienenitriles and isocyanides.

An efficient and divergent one-pot synthesis of 2,3-dihydro-1H-pyrroles, 3-alkyl-1H-pyrroles and 3-alkenyl-1H-pyrroles from readily accessible 2,4-pentadienenitriles with isocyanide based on reaction condition selection has been described. The reaction of 2,4-pentadienenitriles with ethyl isocyanoacetate undergoes a formal [2 + 3] annulation either to generate 2,3-dihydro-1H-pyrroles in the presence of DBU (0.3 equiv.) in EtOH at room temperature or to give 3-alkyl-1H-pyrroles in the presence of DBU (2.0 equiv.) in EtOH under reflux. Moreover, the 2,3-dihydro-1H-pyrroles could be converted to 3-alkenyl-1H-pyrroles with DDQ as an oxidant.

Polymer brushes on planar TiO2 substrates.

A facile and universal method is presented for the preparation of polymer brushes on amorphous TiO2 film. Homogeneous and stable poly(methyl methacrylate), polystyrene, poly(4-vinylpyridine), and poly(N-vinyl imidazole) (PNVI) brushes up to 550 nm are directly created onto TiO2 via UV-induced photopolymerization of corresponding monomers. Kinetic studies reveal a linear increase in thickness with the polymerization time. Characterization of the resulting polymer brushes by FTIR spectroscopy, X-ray photoelectron spectroscopy, contact angle, and atomic force microscopy (AFM) indicates an efficient UV-grafting reaction. Finally, we have demonstrated the possibility in converting the PNVI brushes to poly(vinyl imidazolium bromide), i.e., poly(ionic liquid) brushes by polymer-analogous reactions.

A copper-catalyzed formal O-H insertion reaction of α-diazo-1,3-dicarbonyl compounds to carboxylic acids with the assistance of isocyanide.

A novel copper-catalyzed formal O-H insertion of α-diazo-1,3-dicarbonyl compounds to carboxylic acids has been developed, providing a straightforward synthetic method for α-acyloxy-1,3-dicarbonyl compounds, in which the activation of carboxylic acids by isocyanide plays a crucial role.

Tandem halogenation/Michael-initiated ring-closing reaction of α,ß-unsaturated nitriles and activated methylene compounds: one-pot diastereoselective synthesis of functionalized cyclopropanes.

An efficient one-pot synthetic route to highly substituted cyclopropanes has been developed from readily available α,ß-unsaturated nitriles and doubly activated methylene compounds under very mild conditions in a highly diastereoselective manner, which involves halogenation, Michael addition and intramolecular ring-closing reaction sequences.

Copper-catalyzed three-component reaction: solvent-controlled regioselective synthesis of 4-amino- and 6-amino-2-iminopyridines.

Regioselective synthesis of multisubstituted 4-amino- and 6-amino-2-iminopyridines has been developed via the copper-catalyzed three-component reaction based on the reaction conditions selection. The reaction of sulfonyl azides, alkynes, and 2-[(amino)methylene]malononitriles catalyzed by copper(I) iodide in tetrahydrofuran at room temperature afforded substituted 4-amino-2-iminopyridines, whereas, in N,N-dimethylformamide at 50 °C under N2, it generated substituted 6-amino-2-iminopyridines as predominant products.

Formal [4+1] annulation of α,α-dialkyl ß-oxo amides and dimethylsulfoxonium methylide: a synthetic route to ß-hydroxy-γ-lactams.

A facile and efficient one-pot synthesis of ß-hydroxy-γ-lactams from α,α-dialkyl ß-oxo amides and trimethylsulfoxonium iodide in the presence of sodium hydride via a tandem Corey-Chaykovsky reaction and an intramolecular lactamization process is developed.

Hydrogen bond-assisted 6π-azaelectrocyclization of penta-2,4-dienamides: synthesis of dihydropyridin-2(3H)-ones.

A facile and efficient synthesis of substituted dihydropyridin-2(3H)-ones is developed from penta-2,4-dienamides, in which an intramolecular C-N bond was formed through thermal 6π-azaelectrocyclization. The intramolecular hydrogen bonding-assisted cyclization reaction opens access to a variety of dihydropyridin-2(3H)-ones.

[5C + 1N] annulations: two novel routes to substituted dihydrofuro[3,2-c]pyridines.

Two novel routes based on [5C + 1N] annulations for the synthesis of 2,3-dihydrofuro[3,2-c]pyridines are described. Ammonium acetate (NH(4)OAc) is used as an ammonia source in both routes. The first route utilizes 1-acyl-1-[(dimethylamino)alkenoyl]cyclopropanes as a five-carbon 1,5-bielectrophilic species and combines the [5C + 1N] annulation and regioselective ring-enlargement of cyclopropyl ketone into one pot, whereas the second route utilizes 3-acyl-2-[(dimethylamino)alkenyl]-4,5-dihydrofurans as the five-carbon synthons, which involves a sequential intermolecular aza-addition, intramolecular aza-nucleophilic addition/elimination, and dehydration reaction.

Intramolecular hydrogen bonding-assisted cyclocondensation of α-diazoketones with various amines: a strategy for highly efficient Wolff 1,2,3-triazole synthesis.

A catalytic and highly efficient Wolff's cyclocondensation of α-diazoketones with aromatic and aliphatic amines has been realized for the first time by utilizing the strategy of an intramolecular hydrogen bonding-activating carbonyl group. This approach successfully solved the challenging problem of poor condensation efficiency in Wolff 1,2,3-triazole synthesis, and constitutes a powerful method for the synthesis of highly functionalized 1,2,3-triazoles.

Lawesson's reagent-initiated domino reaction of aminopropenoyl cyclopropanes: synthesis of thieno[3,2-c]pyridinones.

A convenient and efficient synthesis of substituted 2,3-dihydrothieno[3,2-c]pyridin-4(5H)-ones has been developed and relies upon a domino reaction of dimethylaminopropenoyl cyclopropanes initiated by Lawesson's reagent. A mechanism involving regioselective thionation, ring-enlargement, and an intramolecular aza-cyclization sequence is proposed. This protocol was utilized as a one-pot route to thieno[3,2-c]pyridin-4(5H)-ones with DDQ as an oxidant.

Vilsmeier reaction of 3-aminopropenamides: one-pot synthesis of pyrimidin-4(3H)-ones.

A facile one-pot synthesis of pyrimidin-4(3H)-ones was developed via reactions of a series of readily available 3-aminopropenamides with varied Vilsmeier reagents, and a mechanism involving sequential halogenation, formylation, and intramolecular nucleophilic cyclization is proposed.

PIFA-mediated oxidative cyclization of 1-carbamoyl-1-oximylcycloalkanes: synthesis of spiro-fused pyrazolin-5-one N-oxides.

A convenient and efficient synthesis of spiro-fused pyrazolin-5-one N-oxides starting from readily available 1-carbamoyl-1-oximylcycloalkanes is developed. This general protocol features a novel and facile way for access to the five-membered azaheterocycles by formation of a new N-N single bond. The key cyclization step utilizes the formation of an N-oxonitrenium intermediate, mediated by the hypervalent iodine reagent PIFA, and its subsequent intramolecular trapping by the amide moiety under rather mild experimental conditions.

Efficient and divergent synthesis of cyclophosphamide analogues from 2-arylamino-3-acetyl-5,6-dihydro-4H-pyrans.

A facile and efficient one-pot synthesis of substituted cyclophosphamidic chlorides and their analogues has been developed from readily available enaminones, 2-arylamino-3-acetyl-5,6-dihydro-4H-pyrans.

Ring-enlargement of dimethylaminopropenoyl cyclopropanes: an efficient route to substituted 2,3-dihydrofurans.

A convenient and efficient synthesis of substituted dihydrofurans is developed via ring-enlargement of 1-dimethylaminopropenoyl-1-carbamoyl/benzoyl cyclopropanes catalyzed by ammonium acetate in acetic acid with high regio- and stereoselectivity. Some of the newly synthesized substituted dihydrofurans are subjected to further synthetic transformation in the presence of NaOH (aq) in ethanol to afford the corresponding 5-aryl-2,3-dihydrofuro[3,2-c]pyridin-4(5H)-ones in high yields.