Cobalt-Catalyzed Borylative Reduction of Azobenzenes to Hydrazobenzenes via a Diborylated-Hydrazine Intermediate.

Cobalt-catalyzed borylative reduction of azobenzenes using pinacolborane is developed. The simple cobalt chloride catalyst and reaction conditions make this protocol attractive for hydrazobenzene synthesis. This borylative reduction shows good functional group compatibility and can be readily scaled up to the gram scale. Preliminary mechanistic studies clarified the proton source of the hydrazine products. This cobalt-catalyzed azobenzene borylative reaction provides a practical protocol to prepare synthetically useful diborylated hydrazines.

Lanthanide/B(C6F5)3-Promoted Hydroboration Reduction of Indoles and Quinolines with Pinacolborane.

We have developed a lanthanide/B(C6F5)3-promoted hydroboration reduction of indoles and quinolines with pinacolborane (HBpin). This reaction provides streamlined access to a range of nitrogen-containing compounds in moderate to excellent yields. Large-scale synthesis and further transformations to bioactive compounds indicate that the method has potential practical applications. Preliminary mechanistic studies suggest that amine additives promote the formation of indole-borane intermediates, and the lanthanide/B(C6F5)3-promoted hydroboration reduction proceeds via hydroboration of indole-borane intermediates with HBpin and in situ-formed BH3 species, followed by the protodeborylation process.

Iodine-Mediated Oxidative Annulation of ß,γ-Unsaturated Hydrazones in Dimethyl Sulfoxide: A Strategy to Build 1,6-Dihydropyridazines and Pyrroles.

Simple, commercially available iodine was successfully employed as a highly efficient and chemoselective catalyst for the oxidative annulation of ß,γ-unsaturated hydrazones to produce 1,6-dihydropyridazines under mild conditions for the first time. Interestingly, when active ß,γ-unsaturated hydrazone compounds containing electron-donating groups, such as furyl, thienyl, and cycloalkyl, were used, pyrroles were obtained. A gram-scale preparation experiment and further derivatization of pyridazines demonstrated the potential applicability of our synthesis method. Experimental studies and density functional theory calculations unveiled the origin of the chemoselectivity determining the formation of different products.

t BuOLi-Promoted Hydroboration of Esters and Epoxides.

Commercially available and inexpensive lithium tert-butoxide ( t BuOLi) acts as a good precatalyst for the hydroboration of esters, lactones, and epoxides using pinacolborane as a borylation agent. Functional groups such as cyano-, nitro-, amino-, vinyl, and alkynyl are unaffected under the presented hydroboration process, representing high chemoselectivity. This transformation has also been effectively applied to the synthesis of key intermediates of Erlotinib and Cinacalcet. Preliminary investigations of the mechanism show that the hydroboration proceeds through the in situ formed BH3 species.

Hexamethyldisilazane Lithium (LiHMDS)-Promoted Hydroboration of Alkynes and Alkenes with Pinacolborane.

Lithium-promoted hydroboration of alkynes and alkenes using commercially available hexamethyldisilazane lithium as a precatalyst and HBpin as a hydride source has been developed. This method will be appealing for organic synthesis because of its remarkable substrate tolerance and good yields. Mechanistic studies revealed that the hydroboration proceeds through the in situ-formed BH3 species, which acts to drive the turnover of the hydroboration of alkynes and alkenes.

Finite element analysis of fixation effect for femoral neck fracture under different fixation configurations.

In this study, the biomechanical differences among three internal fixation configurations for treatment of Pauwels type II and III femoral neck fractures were analyzed. Using finite element analysis, the femur displacement and stress distributions of the internal fixation device and fracture section were obtained for different patients and movement conditions. The results show that patients with osteoporosis are more prone to femoral varus and femoral neck shortening, and the fracture probability of the device for these patients is higher than that for patients with normal bone. The treatment effect of the inverted-triangle screw (ITS) fixation and proximal femoral nail anti-rotation (PFNA) fixation is better than that of dynamic hip screw (DHS) fixation. The ITS fixation is more suitable for the treatment of the normal bone patients with Pauwels II femur neck fracture. However, the PFNA fixation has better biomechanical advantages and better capability for anti-femoral neck shortening. Therefore, it is suitable for the treatment of femoral neck fracture patients with osteoporosis.

Palladium-Catalyzed Three-Component Cascade Reaction of Nitriles: Synthesis of 2-Arylquinoline-4-carboxylates.

A new method for converting easy availability starting materials 2-(2-oxoindolin-3-yl)acetonitrile, arylboronic acids, and alcohols into 2-arylquinoline-4-carboxylates is reported. The procedure involves a three-component addition/ring expansion/esterification reaction in the presence of Pd(II) catalyst with high functional group tolerance under mild conditions. In addition, the photophysical properties of the resulting product were investigated and exhibited excellent polarity-sensitive fluorescence properties and AIE property.

Synthesis of Imidazoles and Oxazoles via a Palladium-Catalyzed Decarboxylative Addition/Cyclization Reaction Sequence of Aromatic Carboxylic Acids with Functionalized Aliphatic Nitriles.

We herein report an efficient approach for the assembly of multiply substituted imidazoles and oxazoles in a single-step manner. These transformations are based on a decarboxylation addition and annulation of readily accessible aromatic carboxylic acids and aliphatic nitriles and exhibit good functional group compatibility and a high step economy. The reaction is scalable, and as-prepared products could be transformed into practical skeletons. Importantly, the late-stage derivatization of Momelotinib highlights the potential utility of this methodology.

Mg2TiO4 spinel modified by nitrogen doping as a Visible-Light-Active photocatalyst for antibacterial activity.

Nitrogen doped Mg2TiO4 spinel, i.e. Mg2TiO4-xNy, has been synthesized and investigated as a photocatalyst for antibacterial activity. Mg2TiO4-xNy demonstrates superior photocatalytic activity for E. coli disinfection under visible light illumination (λ ≥ 400 nm). Complete disinfection of E. coli at a bacterial cell density of 1.0 × 107 CFU mL-1 can be achieved within merely 60 min. Mg2TiO4-xNy is capable of generating superoxide radicals (•O2 -) under visible light illumination which are the reactive oxygen species (ROSs) for bacteria disinfection. DFT calculations have verified the importance of nitrogen dopants in improving the visible light sensitivity of Mg2TiO4-xNy. The facile synthesis, low cost, good biocompatibility and high disinfection activity of Mg2TiO4-xNy warrant promising applications in the field of water purification and antibacterial products.

Palladium-catalyzed C-H activation of simple arenes and cascade reaction with nitriles: access to 2,4,5-trisubstituted oxazoles.

An efficient and straightforward protocol for the assembly of the pharmaceutically and biologically valuable oxazole skeleton is achieved for the first time from readily available simple arenes and functionalized aliphatic nitriles. This transformation involves palladium-catalyzed C-H activation, carbopalladation and a tandem annulation sequence in one pot. Notably, the reaction proceeds efficiently under redox-neutral conditions, and exhibits high atom-economy. Deuterium-labeling experiments suggested that C-H bond cleavage of the simple arenes might be the rate-determining step.

Selective Synthesis of ß-Ketonitriles via Catalytic Carbopalladation of Dinitriles.

A practical, convenient, and highly selective method of synthesizing ß-ketonitriles from the Pd-catalyzed addition of organoboron reagents to dinitriles has been developed. This method provides excellent functional-group tolerance, a broad scope of substrates, and the convenience of using commercially available substrates. The method is expected to show further utility in future synthetic procedures.

Synthesis of 3-Selenylindoles through Organoselenium-Promoted Selenocyclization of 2-Vinylaniline.

A novel metal-free one-pot protocol for the synthesis of potential biologically active molecules 3-selenylindoles via intramolecular cyclization/selenylation with simple 2-vinylaniline has been developed with moderate to good yield, thus representing it as a facile route to diverse substitution patterns around the indole core. The reaction proceeded smoothly with a broad substrate scope and excellent functional group tolerance. Moreover, the present synthetic route could be readily scaled up to gram quantity without difficulty. Mechanistic studies have revealed that in situ formed selenium electrophile species may be the key intermediate for the selenocyclization process.

Pd-Catalyzed Approach for Assembling 9-Arylacridines via a Cascade Tandem Reaction of 2-(Arylamino)benzonitrile with Arylboronic Acids in Water.

A novel palladium-catalyzed protocol for the synthesis of 9-arylacridines via tandem reaction of 2-(arylamino)benzonitrile with arylboronic acids in water has been developed with good functional group tolerance. The present synthetic route could be readily scaled up to gram quantity without difficulty. This methodology was further extended to the synthesis of a 4'-OH derivative, which showed estrogenic biological activity. Preliminary mechanistic experiments showed that this transformation involves a nucleophilic addition of aryl palladium species to the nitrile to generate an aryl ketone intermediate followed by an intramolecular Friedel-Crafts acylation and dehydration to acridines.

Palladium-Catalyzed Tandem C-C Activation/Cyclization Induced by Carbopalladation of Functionalized Nitriles: Synthesis of Benzo Dipyrromethenes.

A palladium-catalyzed carbon-carbon bond activation-initiated reaction of 2-(3-phenyloxiran-2-yl)benzonitriles with arylboronic acids is reported. Multiple chemical bonds were cleavaged and reconstructed via ß-carbon elimination in this reaction, enabling the construction of valuable benzo-fused dipyrromethenes that are difficult to prepare by other methods. Additionally, a series of benzannulated boron dipyrromethenes are synthesized and show practical significance in terms of expanding the applications and types of fluorescent materials. The proposed mechanism is supported by preliminary mechanistic experiments.

Flexible Capacitive Humidity Sensors Based on Ionic Conductive Wood-Derived Cellulose Nanopapers.

With the growing requirements for the renewability and sustainability of electronic products, environmentally friendly cellulose-based materials have attracted immense research interests and gained increasing prominence for electronic devices. Humidity sensors play an essential role in industries, agriculture, climatology, medical services, and daily life. Here, for the first time, we fabricate capacitive humidity sensors based on ionic conductive wood-derived cellulose nanopapers (WCNs). The WCN-based humidity sensors exhibited ultrahigh sensitivity, fast response, small hysteresis, and more importantly, a wide working range of relative humidity (RH). The sensors showed >104 times increase in the sensing signal over the 7-94% RH range at 20 Hz, while many reported humidity sensors with high sensitivity often have the working range limited to high RH levels. Our sensors can realize the distinction of nuances in humidity and exhibit outstanding noncontact skin humidity sensing properties. Flexible WCN-based humidity sensors were also fabricated, and they displayed excellent sensing properties with long-time stability, endowing them with multifunctional applications. The contrast humidity sensing experiment compared to the existing commercial humidity sensor further demonstrated the higher and faster response of our WCN-based sensors. Thus, this work provides effective guidance for the design of high-performance humidity sensors using nanopapers and opens a new dimension for a variety of future applications.

Palladium-Catalyzed Cascade Reactions of δ-Ketonitriles with Arylboronic Acids: Synthesis of Pyridines.

This study presents the first example of the Pd-catalyzed cascade reactions of 5-oxohexanenitrile with arylboronic acids, affording important synthon 2-methylpyridines that can be further translated through C(sp3)-H functionalization to construct pyridine derivatives. Furthermore, this chemistry allows 5-oxo-5-arylpentanenitrile to react with arylboronic acids to provide unsymmetrical 2,6-diarylpyridines. This protocol paves the way for the practical and atom economical syntheses of valuable pyridines with broad functional groups in moderate to excellent yields under mild conditions.

Homoleptic Bis(trimethylsilyl)amides of Yttrium Complexes Catalyzed Hydroboration Reduction of Amides to Amines.

Homoleptic lanthanide complex Y[N(TMS)2]3 is an efficient homogeneous catalyst for the hydroboration reduction of secondary amides and tertiary amides to corresponding amines. A series of amides containing different functional groups such as cyano, nitro, and vinyl groups were found to be well-tolerated. This transformation has also been nicely applied to the synthesis of indoles and piribedil. Detailed isotopic labeling experiments, control experiments, and kinetic studies provided cumulative evidence to elucidate the reaction mechanism.

Tandem addition/cyclization for synthesis of 2-aroyl benzofurans and 2-aroyl indoles by carbopalladation of nitriles.

The first example of the palladium-catalyzed tandem addition/cyclization of 2-(2-acylphenoxy)acetonitriles with arylboronic acids has been developed, providing a new strategy for the synthesis of 2-aroyl benzofurans with excellent chemoselectivity and wide functional group compatibility. Preliminary mechanistic experiments indicate that this tandem process involves sequential nucleophilic addition generating 2-(2-acylphenoxy)-1-phenylethan-1-one followed by an intramolecular cyclization. This methodology has also been applied to the synthesis of 2-aroyl indoles and the potent CYP19 inhibitor 1-(benzofuran-2-yl(phenyl)methyl)-1H-1,2,4-triazole.

Palladium-Catalyzed Cascade Reactions of 2-(Cyanomethoxy)chalcones with Arylboronic Acids: Selective Synthesis of Emissive Benzofuro[2,3-c]pyridines.

The Pd(II)-catalyzed cascade reactions of 2-(cyanomethoxy)chalcones with arylboronic acids were demonstrated, allowing the rapid construction of benzofuro[2,3-c]pyridine skeletons with excellent selectivity. These transformations involve the domino-style formation of C-C/C-C/C-N bonds through nitrile carbopalladation, intramolecular Michael addition, cyclization, and aromatization. This chemistry allows for the reactions of 2-(cyanomethoxy)chalcones with thiophen-3-ylboronic acid, providing 3-aryl-1-(thiophen-3-yl)benzofuro[2,3-c]pyridines in moderate to good yields. In addition, the resulting products represent a new class of emissive fluorophores.

Syntheses of Pyrroles, Pyridines, and Ketonitriles via Catalytic Carbopalladation of Dinitriles.

The first example of the Pd-catalyzed addition of organoboron reagents to dinitriles, as an efficient means of preparing 2,5-diarylpyrroles and 2,6-diarylpyridines, has been discussed here. Furthermore, the highly selective carbopalladation of dinitriles with organoboron reagents to give long-chain ketonitriles has been developed as well. Based on the broad scope of substrates, excellent functional group tolerance, and use of commercially available substrates, the Pd-catalyzed addition reaction of arylboronic acid and dinitriles is expected to be significant in future synthetic procedures.