Palladium-Catalyzed Three-Component Cascade Carbonylation Reaction to Construct Benzofuran Derivatives.

A novel three-component cyclization carbonylation reaction of iodoarene-tethered propargyl ethers with amine and CO is reported. This palladium-catalyzed cascade reaction undergoes a sequence of oxidative addition, unsaturated bond migration, carbonyl insertion, and nucleophilic attack to deliver the benzofuran skeleton. Both aromatic amines and aliphatic amines could proceed smoothly in this transformation under one atm of CO.

Fluoride-Mediated Aryne 1,2-Difunctionalization Involving C═S Bond Heterolysis.

We have successfully synthesized a series of bidentate ligands by utilizing 2-(trimethylsilyl)phenyl trifluorosulfonate as a precursor for the benzyl group. This method proceeded by inserting a polythiourea into the C═S π-bond, intramolecular ring proton migration, and ring opening. Salient features of this strategy are mild reaction conditions, a novel product structure, excellent stereochemistry, and a good functional group tolerance. Furthermore, a series of density functional theory calculations were performed to gain insights into the transfer mechanism.

Nickel-Catalyzed Three-Component Tandem Radical Cyclization 1,5-Difunctionalization of 1,3-Enynes and Alkyl Bromide.

A nickel-catalyzed three-component tandem radical cyclization reaction of aryl bromides with 1,3-enynes and aryl boric acids to construct γ-lactam-substituted allene derivatives has been described. This protocol provides lactam alkyl radicals through the free radical cyclization process, which can be effectively used to participate in the subsequent multicomponent coupling reaction so that 1,3-enynes could directly convert into corresponding poly-substituted allene compounds. In addition, this efficient method enjoys a broad substrate scope and provides a series of 1,5-difunctionalized allenes in a one-pot reaction.

Synthesis of C4-Aminated Carbazoles and Their Derivatives via Pd/NBE Chemistry.

Carbazole, as one of the most important organic frameworks, has been used in optoelectronic materials and biochemistry. However, the synthesis of C4-substituted carbazole has always been an unsolved problem. This report describes the one-step synthesis of C4-aminated carbazoles and their derivatives through the series reaction of C-H amination and arylation. The substrate scope is wide. C4-Amino carbazoles substituted by C2, C6, C7, and C8 methyl groups, especially carbazole derivatives of fused rings, pyridine, and dibenzofuran, can be synthesized.

Template Synthesis to Solve the Unreachable Ortho C-H Functionalization Reaction of Aryl Iodide.

This report describes the use of a simple Pd/NBE catalytic system to achieve ortho C-H oxylation and phosphonylation and other functionalizations of aryl iodide through templated conversion reactions. Dimethylamine is introduced in the ortho-site of aryl iodide through C-H amination, and aryl dimethylamine is quickly converted to methyl quaternary ammonium salt precipitation. Methyl quaternary ammonium salt avoids Hofmann elimination in subsequent functionalization. This method solves various ortho functionalization reactions of aryl iodide that have not been achieved for a long time in the field of Pd/NBE chemistry indirectly.

Direct synthesis of phosphorotrithioates from [TBA][P(SiCl3)2] and disulfides.

Sulfur-containing organophosphorus molecules have played a pivotal role in organic synthesis, pharmaceutical pesticides and functional materials, thereby motivating researchers worldwide to establish S-P bonds from more environmentally friendly phosphorus sources. In this study, a novel method was developed for constructing S-P bonds, specifically by reacting the inorganic phosphorus derivative TBA[P(SiCl3)2] with sulfur-containing compounds under mild conditions. This method demonstrates the advantages of low energy consumption, mild reaction conditions and environmental friendliness. Moreover, this protocol-as a green synthesis method to replace the use of white phosphorus in the production of organophosphorus compounds (OPCs)-achieved the functional conversion of "inorganic phosphorus to organic phosphorus", in line with the national green development strategy.

Synthesis of 3(2H)-furanone derivatives: p-TsOH/halotrimethylsilane promoted cycloketonization of γ-hydroxyl ynones.

A p-TsOH/halotrimethylsilane facilitated cycloketonization of γ-hydroxyl ynones is detailed. This methodology enables the one-step synthesis of polysubstituted 3(2H)-furanone products. It is remarkable that the reaction exhibits excellent regio- and chemoselectivity by the addition of very small quantities of p-toluenesulfonic acid and water.

N,N-Diisopropylethylamine-Mediated Electrochemical Reduction of Azobenzenes in Dichloromethane.

We report a cathodic reduction-dominated electrochemical approach for the hydrogenation of azobenzenes in dichloromethane. With cheap and readily available N,N-diisopropylethylamine as a catalytic mediator, the reaction proceeded smoothly in a simple undivided cell under constant-current electrolysis. A series of azobenzenes were successfully reduced to the corresponding hydrazobenzenes in moderate to high yields at room temperature. Preliminarily mechanistic studies indicate that solvent dichloromethane acts as a hydrogen source. The use of a common solvent as a hydrogen source, no need for stoichiometric mediators or metallic reductants, and mild conditions make this work a more straightforward and sustainable protocol for hydrogenation of azobenzenes.

Visible light-promoted intermolecular cyclization/aromatization of chalcones and 2-mercaptobenzimidazoles via an EDA complex and a mechanism study.

Visible-light-promoted cyclization and aromatization of chalcones with 2-mercaptobenzimidazoles have been successfully developed to obtain diverse imidazo[2,1-b]thiazoles, and C-S and C-N bonds were constructed in one step. The reaction uses oxygen in the air as an oxidant, and the method does not need an external photocatalyst or a transition metal catalyst. The strategy features mild conditions, a simple system, readily accessible feedstocks, and a friendly environment. UV absorption spectroscopy and control experiments have shown that the reaction mechanism involves the formation of an electron-donor-acceptor (EDA) complex from thiolate anions and chalcones. In order to verify the mechanism, we studied the structure and HOMO/LUMO of the EDA complex by density functional theory (DFT) calculations. The results show that the π-π stacking between chalcones and 2-mercaptobenzimidazoles will cause a red shift of the UV absorption wavelength in the presence of Cs2CO3, and also provide a theoretical basis for the electron transfer of EDA complexes.

Visible-Light-Promoted Diboron-Mediated Transfer Hydrogenation of Azobenzenes to Hydrazobenzenes.

A visible-light-promoted transfer hydrogenation of azobenzenes has been developed. In the presence of B2pin2 and upon visible-light irradiation, the reactions proceeded smoothly in methanol at ambient temperature. The azobenzenes with diverse functional groups have been reduced to the corresponding hydrazobenzenes with a yield of up to 96%. Preliminary mechanistic studies indicated that the hydrogen atom comes from the solvent and the transformation is achieved through a radical pathway.

Synthesis, structural characterization, molecular docking study, biological activity of carbon monoxide release molecules as potent antitumor agents.

In this study, two series of novel carbon monoxide-releasing molecules (CO-RMs) containing Co were designed and synthesized. The synthesized complexes were characterized by IR, ESI-MS, 1H NMR and 13C NMR spectroscopies. The antitumor activity of all complexes on HepG2 cells, Hela cells and MDA-MB-231 cells were assayed by MTT. IC50 values of complexes 1-13 were 4.7-548.6 µM. Among these complexes, complex 1 was presented with a high selectivity to HepG2 cells (IC50 = 4.7 ± 0.76 µM). Compared with iCORM (inactive CORM), CORM (complex 1) showed a remarkable activity against tumor cells owing to co-effect of CO and the ligand of COX-2 inhibitor. In addition, complex 1 increased ROS in mitochondria and caused a decrease of dose-dependent mitochondrial membrane potential against HepG2 cells. Complex 1 down-regulated the expression of COX-2 protein in western blot analysis. The molecular docking study suggested that the complex 1 formed a hydrogen bond with amino acid R120 in the active site of the Human cyclooxygenase-2 (COX-2). Therefore, the complex 1 could induce apoptosis of HepG2 cells through targeting COX-2 and mitochondria pathways, and it maybe a potential therapeutic agent for cancer.

AgSCF3/Na2S2O8-Promoted Trifluoromethylthiolation/Cyclization of o-Propargyl Arylazides/ o-Alkynyl Benzylazides: Synthesis of SCF3-Substituted Quinolines and Isoquinolines.

A AgSCF3/Na2S2O8-promoted trifluoromethylthiolation/cascade cyclization of o-propargyl arylazides (or o-alkynyl benzylazides) triggered by a carbon-carbon triple bond is reported. This strategy provides the synthesis of valuable SCF3-substituted quinoline and isoquinoline systems via the construction of one C(sp2)-SCF3 bond and one C-N bond within one process.

The solvent-controlled chemoselective construction of C-S/S-S bonds via the Michael reaction/thiol coupling of quinoline-2-thiones.

K2CO3-catalyzed thio-Michael addition using quinoline-2-thiones and α,ß-unsaturated carbonyl compounds was used to assess the chemoselective construction of C-S and S-S bonds under mild reaction conditions in different solvents. The C-S bond showed a better chemoselective construction in EtOH whereas the S-S bond showed a better chemoselective construction in 1,4-dioxane. The corresponding products, generated from the reaction, presented a significant solvent-controlling effect.

Efficient synthesis of esters through oxone-catalyzed dehydrogenation of carboxylic acids and alcohols.

Since esters are important organic synthesis intermediates, an environmentally friendly oxone catalyzed-esterification of carboxylic acids with alcohols has been developed. A series of carboxylic acid esters are obtained in high yield. This strategy requires mild reaction conditions, providing an attractive alternative for the construction of valuable carbonyl esters. Electron-rich and electron-deficient groups are compatible with the standard conditions and a variety of substrates are demonstrated. Moreover, the reaction could easily be adapted to typical prodrugs, drugs and gram-scale synthesis.

An Efficient Amide-Aldehyde-Alkene Condensation: Synthesis for the N-Allyl Amides.

The allylamine skeleton represents a significant class of biologically active nitrogen compounds that are found in various natural products and drugs with well-recognized pharmacological properties. In this personal account, we will briefly discuss the synthesis of allylamine skeletons. We will focus on showing a general protocol for Lewis acid-catalyzed N-allylation of electron-poor N-heterocyclic amides and sulfonamide via an amide-aldehyde-alkene condensation reaction. The substrate scope with respect to N-heterocyclic amides, aldehydes, and alkenes will be discussed. This method is also capable of preparing the Naftifine motif from N-methyl-1-naphthamide or methyl (naphthalene-1-ylmethyl)carbamate, with paraformaldehyde and styrene in a one-pot manner.

Copper(i) chloride promoted Csp(2)-N cross-coupling of 1,2-di(pyrimidin-2-yl) disulfides with amines: an efficient approach to obtain C2-amino functionalized pyrimidines.

The copper(i)-promoted cross-coupling of 1,2-di(pyrimidin-2-yl) disulfides with aromatic amines and aliphatic amines to deliver C-N coupling products in moderate to good yields is reported in this paper. Central to this strategy is the conversion of disulfides into aryl- and alkyl amines by a copper-promoted chemoselective C-S bond cleavage.

Hydrazone Phosphaketene as a Synthetic Platform To Obtain Three Classes of 1,2,4-Diazaphosphol Derivatives by Switchable Chemoselectivity Strategies.

We introduce switchable chemoselectivity strategies based on the hydrazone phosphaketene intermediate to synthesize three classes of 1,2,4-diazaphosphol derivatives. First, the five-membered heterocyclic P and O anion intermediates acted as nucleophilic agents in the selective construction of C-P and C-O bonds. Second, the phosphinidene served as a phosphorus synthon, allowing for the formation of C-P and C-N bonds. Finally, a stepwise mechanism, supported by DFT calculations, was invoked to explain the reaction selectivity.

EtOS2K as a C1 Source: Solvent- and Temperature-Controlled Selective Synthesis of Quinoline-2-thione and Quinoline-2-one Derivatives.

Herein, we disclosed a highly chemoselective synthesis of quinoline-2-one and quinoline-2-thione derivatives using EtOS2K as the C1 source. Quinoline-2-one derivatives were synthesized selectively with NaCl as a catalyst in the solvent DMSO/H2O, while quinoline-2-thione derivatives were produced without the need for any catalyst in an environmentally friendly solvent EtOH/H2O. The reaction conditions were mild and had good functional group tolerance.

Direct Synthesis of C4-Acyl Indoles via C-H Acylation.

The direct synthesis of C4-acyl indoles deprived of C2 and C3 substituents has proven to be challenging, with scarce efficient synthetic routes being reported. Herein, we disclose a highly site-selective palladium-catalyzed C-H acylation for the construction of C4-acyl indoles via a Catellani-Lautens cyclization strategy. In addition, we systematically studied the ortho C-H acylation mechanism of iodoaniline through density functional theory (DFT) calculations and combined experimental results to elucidate the principle of high chemoselectivity brought by triazine benzoate as an acylation reagent.

Chemical characteristics of normal, woolly apple aphid-damaged, and mechanically damaged twigs of six apple cultivars, measured in autumn wood.

Chemical characteristics of normal, woolly apple aphid-damaged, and mechanically damaged twigs of six apple cultivars: Red Fuji, Golden Delicious, Qinguan, Zhaojin 108, Starkrimson, and Red General, were examined in autumn wood to provide abetter understanding of factors related to cultivar resistance to the woolly apple aphid, Eriosoma lanigerum (Hausmann). Chemical measures examined included soluble sugars, soluble proteins and amino acids, total phenolics, and polyphenol oxidase (that enhances the resistance of plants to insects) and superoxide dismutase, peroxidase, and catalase (that degrade waste products in plants). Soluble sugar, protein, and amino acid contents in normal (undamaged) twigs of Red Fuji, aphid-susceptible cultivar, were higher than in mechanically damaged and aphid-damaged twigs. Total phenolic compounds, an important group of defensive compounds against aphids, increased by 30.5 and 6.0% in mechanically damaged twigs of Qinguan and Zhaojin 108, respectively, and decreased by 21.7 and 16.1% in aphid-damaged twigs of Red Fuji and Red General, respectively. Compared with normal twigs, in aphid-damaged twigs, superoxide dismutase, peroxidase, and polyphenol activity all decreased in Red Fuji. The resistance of some apple cultivars to woolly apple aphid during the growth of autumn shoots was related to several of the physiological indices we monitored. The thin epidermis of callus tissue over healed wounds showed increased susceptibility to the attack by woolly apple aphid. Apple cultivar Qinguan with the highest level of resistance to woolly apple aphid in autumn had increased in amino acid, total phenolic compound levels, and enzyme activity after aphid feeding.