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We describe a nickel-catalyzed carbonylative cross-coupling of unactivated secondary alkyl electrophiles with the organozinc reagent at atmospheric CO gas, thus allowing the expedient construction of unsymmetric dialkyl ketones with broad functional group tolerance. The leverage of a newly developed NN2-pincer type ligand enables the chemoselective three-component carbonylation by overcoming the competing Negishi coupling, the undesired ß-hydride elimination, and dehalogenation of alkyl iodides side pathways. Both alkyl iodides and alkyl tosylates are compatible in the single electron transfer involved mechanism.
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A nickel-catalyzed acylation of vinylpyridines with CO at atmospheric pressure is reported, allowing for an expedient approach to synthesize ß-acyl pyridine derivatives with high regio- and chemoselectivity. The electron-withdrawing property of pyridine plays pivotal roles in activating the alkenyl group, thereby facilitating this carbonylative process. In addition to vinylpyridines, other alkenylheterocycles such as thiazole and quinoline were also suitable for this method.
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In this paper, we focus on the fourth-order nonlinear Schrödinger equation, which can describe the optical system and the Heisenberg spin system. We consider a continuous wave perturbed by the one-dimensional random rough surface as the initial condition. First, we numerically resolve the eigenvalues under different control parameters utilizing the Fourier collocation method. Then, we simulate the evolution of this equation under the above initial conditions via the symmetrical split-step Fourier method. Moreover, we investigate the "steady" chaotic state by evolving a large number of initial conditions for the same control parameters. We find that the control parameters of the initial condition affect the number and intensity of rogue waves (RWs) in integrable turbulence. In particular, we locate the inflection point where the control parameter affects the velocities of solitons and the inconsistency within the parameter of the contribution to the generation of RWs. We further verify that the collision between breathers, solitons, and breathers and solitons can generate RWs. These results will enable us to understand the turbulent state and the formation mechanism of RWs.
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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.
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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.
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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.
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A novel metal-free catalysis protocol for the synthesis of 1,2-diarylpyrazolo[5,1- b]quinazolin-9(1 H)-ones via intramolecular oxidative C-H amination of ( E)-3-(arylamino)-2-styrylquinazolin-4(3 H)-ones has been developed in moderate to good yield. The method shows good functional group tolerance. The presented approach offers a new synthetic pathway toward the core structures of 2,3-fused quinazolinones. Moreover, the present synthetic route can be readily scaled up to gram quantity without difficulty. A possible mechanism involves a seleniranium ion followed by three-membered ring opening to form the C-N bond.
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The first example of the palladium-catalyzed tandem addition/cyclization of 2-(benzylidenamino)benzonitriles with arylboronic acids has been developed. This transformation features good functional group tolerance and provides an alternative synthetic pathway to access 2,4-diarylquinazolines in moderate to good yields. A plausible mechanism for the formation of 2,4-diarylquinazolines involving sequential nucleophilic addition followed by an intramolecular cyclization is proposed.
Assuntos
Nitrilas/química , Paládio/química , Quinazolinas/química , Fenômenos Bioquímicos , Catálise , CiclizaçãoRESUMO
An efficient protocol to construct 2-arylindoles was developed through palladium-catalyzed tandem addition/cyclization of potassium aryltrifluoroborates with aliphatic nitriles in aqueous medium. The use of water as the reaction medium makes the synthesis process environmentally benign. A plausible mechanism for the formation of 2-arylindoles involving sequential nucleophilic addition followed by an intramolecular cyclization is proposed. Moreover, the utility of this catalytic tandem transformation was also demonstrated in an efficient gram-scale synthesis. This method provides an alternative synthetic tool for accessing a more diverse array of 2-arylindoles.
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Introduction: Burns are a common trauma associated with considerable mortality and morbidity. Although a lot is known regarding burns' pathogenesis, the involvement of ferroptosis is uncertain. Here, we aimed to explore vital ferroptosis-related genes and molecules in burns, through bioinformatics analysis, to uncover new effective therapeutic targets. Methods: The FerrDb database was used to acquire ferroptosis-related genes and GSE19743 was downloaded from Gene Expression Omnibus (GEO), a dataset with analysis of control and burned individuals. Hub genes were selected with Cytoscape software, and Gene Ontology (GO), and Kyoto Encyclopedia of Genes and Genomes (KEGG) enrichment analyses were conducted. Cox proportional hazard function and Kaplan-Meier survival analyses were implemented to screen prognosis-related genes. Additionally, the miRWalk database was used to acquire the miRNAs relevant to our hub genes function and analyzed for enrichment. Result: We identified 64 differentially expressed genes and through the intersection with ferroptosis-related genes, 10 were selected as hub genes. GO analysis revealed that the hub genes' most enriched activities were response to oxidative stress, pyridine-containing compound metabolic processes, and reactive oxygen species metabolic processes. KEGG pathways' analysis showed that these overlapped genes were enriched in several pathways, namely, in VEGF signaling. Furthermore, the molecular miRNA functions significantly enriched were signal transduction and cell communication, namely, the biological pathways of the glypican pathway and the ErbB receptor signaling network. SLC40A1 and GPT2 genes were found to be associated with overall survival, suggesting an important role in burn prognosis. Discussion: This study may improve our understanding of the underlying burn mechanisms and provide a new direction for the prevention of poor outcomes, advances in burns treatment, and drug development.
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The construction of vicinal stereogenic centers via the simultaneous formation of two C-C bonds across alkenes under oxidative conditions is a stubborn challenge. Herein, we report a Pd(II)-catalyzed highly enantioselective intermolecular oxidative 1,2-diarylation reaction of internal enamides with aryl boronic acids, enabling the expedient construction of two vicinal stereocenters with excellent diastereo-, and enantioselectivities.
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Estresse Oxidativo , Paládio , Catálise , Estrutura Molecular , Paládio/química , EstereoisomerismoRESUMO
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.
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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.
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Inspired by the morphology characteristics of the earthworms and the excellent deformability of origami structures, this research creates a novel earthworm-like locomotion robot through exploiting the origami techniques. In this innovation, appropriate actuation mechanisms are incorporated with origami ball structures into the earthworm-like robot 'body', and the earthworm's locomotion mechanism is mimicked to develop a gait generator as the robot 'centralized controller'. The origami ball, which is a periodic repetition of waterbomb units, could output significant bidirectional (axial and radial) deformations in an antagonistic way similar to the earthworm's body segment. Such bidirectional deformability can be strategically programmed by designing the number of constituent units. Experiments also indicate that the origami ball possesses two outstanding mechanical properties that are beneficial to robot development: one is the structural multistability in the axil direction that could contribute to the robot control implementation; and the other is the structural compliance in the radial direction that would increase the robot robustness and applicability. To validate the origami-based innovation, this research designs and constructs three robot segments based on different axial actuators: DC-motor, shape-memory-alloy springs, and pneumatic balloon. Performance evaluations reveal their merits and limitations, and to prove the concept, the DC-motor actuation is selected for building a six-segment robot prototype. Learning from earthworms' fundamental locomotion mechanism-retrograde peristalsis wave, seven gaits are automatically generated; controlled by which, the robot could achieve effective locomotion with qualitatively different modes and a wide range of average speeds. The outcomes of this research could lead to the development of origami locomotion robots with low fabrication costs, high customizability, light weight, good scalability, and excellent re-configurability.