One-pot synthesis of 2-amino-3,4-dicyanopyridines from ketoximes and tetracyanoethylene via Cu(I)-catalyzed cyclization

A novel approach to 2-amino-3,4-dicyanopyridines has been discovered from Cu(I)-catalyzed cyclizations of simple and easily available ketoximes and tetracyanoethylene (TCNE). The complexed radical mechanism involves cleavage of several OH/NO/CH bonds, and new CC/CN bonds formation. A wide variety of substrates with different functional groups could be smoothly converted into the corresponding products in moderate yields.     

Mn(III)-mediated radical cascade reaction of boronic acids with isocyanides: Synthesis of diimide derivatives

A manganese(Ⅲ)-promoted oxidative radical cascade reaction of easily accessible arylboronic acids with isocyanides to construct diimide derivatives was studied. This protocol provides a new way to synthesis of acetyl diimide derivatives. New C-C, C-N and C=O bonds were formed in one step.     

Reprint of: Acid-mediated four-component tandem cyclization: Access to multifused 1,3-benzoxazine frameworks

An acid-mediated multicomponent reaction has been developed for the direct synthesis of multifused 1,3-benzoxazine derivatives from simple and readily available arylglyoxal monohydrates and 2-aminobenzyl alcohols under mild conditions. This novel protocol is proposed to proceed through intramolecular poly-heterocyclizations, thus leading to the formation of three new rings and six new chemical bonds, including four CN and two CO bonds.     

Facile one-pot synthesis of novel highly functionalized dihydro-1H-pyrrole derivatives catalyzed by molecular iodine

An efficient, environmentally benign and molecular iodine promoted protocol was described for cascade synthesis of two kinds of novel dihydro-1H-pyrrole derivatives, 5 and 7. Compounds 5 were prepared via four-component reaction between diethyl acetylenedicarboxylate (DEAD), aromatic amines and phenylglyoxal monohydrate catalyzed by 10 mol% of iodine in ethanol at room temperature. In addition, using same reaction conditions, a three-component reaction between (E)-N-methyl-1-(methylthio)-2-nitroethenamine (NMSM), aromatic amines and arylglyoxal monohydrate was performed to access product 7. These transformations apparently proceed through an imine intermediate followed by iodine induced Mannich reaction and subsequent intra-molecular cyclization sequences. The protocol involves the formation of CN, CC and OH bonds leading to the preparation of a hexa substituted five membered ring with two stereo centres. The syntheses avoid the use of traditional column chromatography and recrystallization purification methods and, hence, follow the group-assisted purification (GAP) chemistry process.     

Reaction pathway change on plasmonic Au nanoparticles studied by surface-enhanced Raman spectroscopy

Gold nanoparticles (Au NPs) are nanoscale sources of light and electrons, which are highly relevant for their extensive applications in the field of photocatalysis. Although a number of research works have been carried out on chemical reactions accelerated by the energetic hot electrons/holes, the possibility of reaction pathway change on the plasmonic Au surfaces has not been reported so far. In this proof-of-concept study, we find that Au NPs change the reaction pathway in photooxidation of alkyne under visible light irradiation. This reaction produces benzil (COCO) without the presence of Au NPs. In contrast, as indicated by surface-enhanced Raman spectroscopic (SERS) results, the CC triple bonds (CC) adsorbed on Au NPs are converted into carboxyl (COOH) and acyl chloride (COCl) groups. The plasmonic Au NPs not only provide energetic charge carriers but also activate the reactant molecules as conventional heterogeneous catalysts. This study discloses the second role of plasmonic NPs in photocatalysis and bridges the gap between plasmon-driven and conventional heterogeneous catalysis.     

Effect of oxygen-containing functional groups on the wettability of coal through DFT and MD simulation

To investigate the wettability of different oxygen-containing functional group (OFG) surfaces, graphite substrates were used as a model for coal adsorbents. The substrates were modified with COOH, OH, CO, and OCH₃. The adsorption-diffusion behavior of H₂O molecules/water droplets on different OFG surfaces was investigated using molecular dynamics (MD) simulations with frontier orbital energy difference as a metric for different surface wettability degrees in quantum chemical analysis. The results indicated that the frontier orbital energy difference of the H₂O molecule was 3.480, 3.491, 3.631, and 3.680 eV for PhCOOH, PhOH, PhCO, and PhOCH₃, respectively. In addition, the equilibrium contact angle, interaction energy, and number of hydrogen bonds after the adsorption equilibrium of water droplets for COOH, OH, CO, and OCH₃ surfaces were 22.34°, ?5.03 kcal/mol, and 652; –23.72°, ?4.19 kcal/mol, and 450; 68.01°, ?0.79 kcal/ mol, and 61; 90.51°, ?0.50 kcal/mol, and 28, respectively. The smaller the energy difference between the frontier orbitals of the H₂O molecule and the OFG, the smaller the equilibrium contact angle between the water droplet and the OFG surface, the more hydrogen bonds were formed, and the larger the absolute value of the interaction energy, the better the wettability of the surface of the OFG. The order of wettability of the different OFG surfaces was COOH > OH > CO > OCH₃, which is consistent with the radial distribution function and the analysis results for the extended area, etc. The results of density functional theory (DFT) calculations and MD simulations exhibited identical patterns, indicating the reasonableness of the simulations. This study may serve as a reference for the suppression of hydrophilicity in low-order coal and the enhancement of the flotation effect.     

Rhodium-catalyzed CH activation/cyclization of enaminones with sulfoxonium ylides toward polysubstituted naphthalenes

A rhodium-catalyzed ortho-CH functionalization and annulation between enaminones and sulfoxonium ylides was developed, affording a series of multi-substituted naphthalenes in good to moderate yields with excellent functional group compatibility. The procedure featured with enaminone acting as both a directing and cyclization bifunctional group, and the application of sulfoxonium ylide in CH functionalization.     

Non-directed highly para-selective CH functionalization of TIPS-protected phenols promoted by a carboxylic acid ligand

Palladium-catalyzed non-directed CH functionalization provides an efficient approach for direct functionalization of arenes, but it usually suffers from poor site selectivity, limiting its wide application. Herein, it is reported for the first time that the carboxylic acid ligand of 3,5-dimethyladamantane-1-carboxylic acid (1-DMAdCO₂H) can affect the site selectivity during the CH activation step in palladium-catalyzed non-directed CH functionalization, leading to highly para-selective CH olefination of TIPS-protected phenols. This transformation displayed good generality in realizing various other para-selective CH functionalization reactions such as halogenation, and allylation reactions. A wide variety of phenol derivatives including bioactive molecules of triclosan, thymol, and propofol, were compatible substrates, leading to the corresponding para-selective products in moderate to good yields. A preliminary mechanism study revealed that the spatial repulsion factor between carboxylic acid ligand and bulky protecting group resulted in the selective CH activation at the less sterically hindered para-position. This new model non-directed para-selective CH functionalization can provide a straightforward route for remote site-selective CH activations.     

Synthesis and properties of π-extended fluoranthene derivatives from 1,2-diarylacenaphthylene derivatives

Acenaphthylene units work as a useful platform for the synthesis of polycyclic aromatic hydrocarbons (PAH). Three 1,2-diarylacenaphthylene derivatives (9-phenanthryl, 7-t-butyl-2-pyrenyl and 2-naphthyl) were prepared by Suzuki-Miyaura coupling of 1,2-dibromoacenaphthylene with the corresponding boronic acids and ester. The Scholl reaction of the phenanthryl derivative affords a donor-acceptor type fluoranthene derivative possessing a hemi-coronene structure by forming two CC bonds between phenanthryl groups. The reaction of the pyrenyl derivative allows one CC bond formation to give a helicene-type fluoranthene derivative. The reaction of the naphthyl derivative provides an asymmetric fluroranthene derivative having an anthracene unit accompanied with one CC bonding reaction, while a photochemical cyclization followed by dehydroaromatization reaction of the compound gives a symmetric fluoranthene derivative with a [5]helicene structure.     

A synthesis of cephalostatin 1

A synthesis of cephalostatin 1 from hecogenin is described in detail. The gram-scale synthesis of south part features a Baeyer–Villiger oxidation of hecogenin to 16,20-diol, a selective oxidation of C16OH with Dess–Martin periodinane, a Rh(I)-catalyzed C15C16 double bond shift to C14C15 position, and a Hg(OAc)₂-mediated spiroketal formation from cyclic enol ethers with alkenyl side chain at 2-position. Key transformations in the synthesis of north part, also on gram scale, include an abnormal Baeyer–Villiger oxidation of hecogenin to the corresponding dinorcholanic lactone, where a catalytic amount of iodine acts as a traceless and catalytic switch, an umpolung of steroidal 22-aldehyde to forge C22C23 bond with good stereochemical control, a cascade spiroketal-forming process to establish DEF rings in one operation, and a selective oxidation of C3OH. There are also other noteworthy transformations that, although not used in our final route, are valuable and could be applied to other syntheses, including: intra- or intermolecular S_N2′ processes of C14-heteroatom-substituted C15C16 alkenes, an unprecedented rearrangement of β-adduct of D-ring dienes and singlet oxygen, a chelation-controlled methylallylation of C23 aldehyde, and so on.     

Advances in amide and thioamide assisted C(sp3)H functionalization

CH activation is gaining substantial attention from synthetic and process chemists in recent years. Regio- and stereo-selective CH functionalization particularly facilitated by carboxylic acids and derivatives as directing groups has been progressing to an extent that this transformation could be conceived as one of the steps to assemble molecules in modern retrosynthetic analysis. This digest paper covers the most recent developments in C(sp³)H functionalization using carboxylic acid derivatives such as amides or thioamides as a directing group and highlights new reaction discoveries and applications. The content of this review is organized based on the types of directing groups and the mechanism by which the C(sp³)H bond is believed to be activated.     

Ru(II)-catalyzed regioselective C-7 hydroxymethylation of indolines with formaldehyde

A regioselective addition of C7H bonds of indolines to formaldehyde is reported to synthesize a variety of C-7 hydroxymethylated indolines via a Ru(II)-catalyzed CH activation. More importantly, a one-pot CH formylation procedure is also developed to synthesize valuable C7-formyl indoles.     

Silica supported potassium oxide catalyst for dehydration of 2-picolinamide to form 2-cyanopyridine

The dehydration of 2-picolinamide to produce 2-cyanopyridine was investigated thoroughly using silica supported potassium oxide as a heterogeneous catalyst. Both large specific surface area and pore size of SiO_2 (B) contributed to the favorable catalytic performance for the synthesis of 2-CP. In addition, the yield of 2-CP showed the linear relationship with the amounts of medium basicity of the catalysts,demonstrating that medium basic sites were the active sites of silica supported potassium oxide catalysts. The catalysts were further characterized by XRD and FT-IR to clarify the active species. The results indicated the Si—O—K group produced by the reaction of K_2CO_3 with Si—OH was the active species, which was further evidenced by the adjustment of the amount of Si—OH by silylation and hydroxylation procedure.     

Copper-catalyzed oxidative CH bond functionalization of N-allylbenzamide for CN and CC bond formation

CH bond functionalization for CN and CC bond formations via cross-dehydrogenative coupling (CDC) of N-allylbenzamides with indole as amine source has been developed under a copper-catalyzed condition. To the best of our knowledge, these are the first examples in which different classes of N-containing compounds were directly prepared from the readily available N-allylbenzamides using an inexpensive catalyst-oxidant (CuSO₄/TBHP) system. Further, it was applied for the synthesis of α-substituted N-allylbenzamides by using Grignard reagent as nucleophiles.     

Ultrasound assisted one-pot synthesis of 1,2-diaryl azaindoles via Pd/C-Cu catalysis: Identification of potential cytotoxic agents

Ultrasound assisted one-pot and direct access to 1,2-diaryl substituted azaindole derivatives has been achieved via the sequential N-arylation followed by coupling-cyclization under Pd/C-Cu catalysis. The methodology involved initial CN bond forming reaction (step 1) between an appropriate o-bromo substituted amino pyridine and iodoarene followed by CC and CN bond formation (step 2) between the resulting N-aryl substituted intermediate and a terminal alkyne in the same pot. A variety of azaindoles was prepared by using this method. These compounds were assessed for their cytotoxic properties against two different metastatic breast cancer cell lines. Compounds 4i, 4k and 4o showed promising growth inhibition of these cell lines and SIRT1 inhibition in vitro.     

Functional groups to modify g-C_3N_4 for improved photocatalytic activity of hydrogen evolution from water splitting

Rational modification by functional groups was regarded as one of efficient methods to improve the photocatalytic performance of graphitic carbon nitride(g-C_3 N_4).Herein,g-C_3 N_4 with yellow(Y-GCN) and brown(C-GCN) were prepared by using the fresh urea and the urea kept for five years,respectively,for the first time.Experimental results show that the H2 production rate of the C-GCN is 39.06 μmol/h,which is about 5 times of the Y-GCN.Meantime,in terms of apparent quantum efficiency(AQ.E) at 420 nm,C-GCN has a value of 6.3% and nearly 7.3 times higher than that of Y-GCN(0.86%).The results of XRD,IR,DRS,and NMR show,different from Y-GCN,a new kind of functional group of —N=CH— was firstly in-situ introduced into the C-GCN,resulting in good visible light absorption,and then markedly improving the photocatalytic performance.DFT calculation also confirms the effect of the —N=CH— group band structure of g-C_3N_4.Furthermore,XPS results demonstrate that the existence of —N=CH— groups in C-GCN results in tight interaction between C-GCN and Pt nanoparticles,and then improves the charge separation and photocatalytic performance.The present work demonstrates a good example of "defect engineering" to modify the intrinsic molecular structure of g-C_3N_4 and provides a new avenue to enhance the photocatalytic activity of g-C_3N_4 via facile and environmental-friendly method.     

Synthesis,physico-chemical characterization,antimicrobial activity and toxicological features of AgZnO nanoparticles

Silver-zinc oxide nanoparticles (AgZnO NPs) were chemically synthesized by the deposition of Ag NPs on the surface of ZnO NPs using silver nitrate, three types of anionic polyelectrolytes and citric acid as reagents. The Wavelength Dispersive X-ray Fluorescence (WDXRF) spectrometry of AgZnO NPs revealed 0.41–0.69 wt% Ag, and balance ZnO. The existence of Ag NPs on the surface of ZnO NPs with hexagonal wurtzite structure was highlighted by X-ray Diffraction (XRD) analysis, scanning electron microscopy (SEM), and Ultraviolet–Visible (UV–Vis) spectroscopy. The diffuse reflectance absorption of AgZnO NPs in the visible light region increased with the increase of Ag NPs content. The Fourier Transform Infrared (FTIR) spectrometry revealed no chemical bonding between Ag NPs and ZnO NPs and confirmed the presence of functional groups characteristic to ZnO and carboxylic acid salts. The newly synthesized AgZnO NPs displayed antimicrobial activity against all the tested medically relevant pathogens, with minimal (biofilm) inhibitory concentrations ranging from 1.875 mg/mL to 7.5 mg/mL. Although the in vitro genotoxicity assay revealed a relatively high micronuclei index, the in vivo micronucleus (MN) test revealed a low MN frequency in animals treated with AgZnO NPs. The histopathological analysis revealed non-significant structural changes of the hepatic parenchyma, renal cortex and intestinal mucosa and minimal inflammatory reactions. The AgZnO NPs administration induced TUNEL positive nuclei of Kupffer cells in the liver parenchyma. The present study shows that the newly synthesized AgZnO NPs are active against planktonic and adherent microorganisms and could be exploited to develop novel antimicrobial strategies for the biotechnology and biomedical fields. Easy scalability of the developed chemical synthesis is a major advantage in producing large batches of AgZnO NPs with reproducible properties.     

Synthesis of core-shell and Janus-like nanoparticles by non-synchronous electrical explosion of two intertwined wires from immiscible metals

Bimetallic nanoparticles with core-shell structure and Janus nanoparticles attract much attention because of their unique properties. In this article we demonstrate the capabilities of an efficient method of synthesizing a wide range of bimetallic nanoparticles by the electrical explosion of two wires made of immiscible metals. To synthesize bimetallic nanoparticles, we have chosen model metals whose liquid phase undergoes lamination only within a limited temperature and concentration interval (CuNb and PbCu) and metals whose components laminate in the liquid state over a wide interval of temperatures and concentrations (AgNi and AgFe). It has been shown that the structure type of the resulting bimetallic nanoparticles (homogeneous distribution of the components, core-shell nanoparticles or Janus nanoparticles) depends on the surface energy and the crystalline structure of the metals.     

I2/TBHP mediated multiple CH bonds functionalization of azaarenes with methylarenes to synthesize iodoisoquinolinones via iodination/N-benzylation/amidation sequence

An oxidative multi-functionalization of azaarenes with benzylic CH bonds of methylarenes via iodination/N-benzylation/amidation cascade, to produce N-benzyl-4-iodoisoquinolin-1(2H)-ones and N-benzyl-3-iodoquinolin-2(1H)-ones is developed. The molecular iodine plays a triple role in activating benzylic sp³ CH bond of methylbenzenes, accelerating the oxidation process and serving as iodination reagent. This reaction utilizes cheap and readily available azaarenes and methylarenes as starting materials and proceeds under metal-free conditions to construct C-I, CN and CO bonds consecutively and afford iodo(iso)quinolinones efficiently.