Nickel-catalyzed umpolung C-S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides

A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl aryl thioethers is described. This reaction features excellent selectivity, wide functionality tolerance, broad substrate scope, and facile late-stage modification of biologically relevant molecules.Mechanistic studies recognize initial generation of an amidyl radical anion via thermoinduced reduction of DMF with Sn, followed by umpolung reduction and single electron transfer of the nucleophilic sulfonyl moiety to form a sulphydryl radical and engage the Ni^(0)/Ni^(Ⅰ)/Ni^(Ⅲ)/Ni^(I) catalytic cycle.

Single-atom Pd catalyst anchored on Zr-based metal-organic polyhedra for Suzuki-Miyaura cross coupling reactions in aqueous media

The challenge for single-atom catalysts in various C-C cross coupling reaction exists in the development of solid supporting materials.It has been desired tofind a supporting material designed in molecular level to anchor a single-atom catalyst and provide high degree of dispersion and substrate access in aqueous media.Here,we prepared discrete cages of metal-organic polyhedra anchoring single Pd atom(MOP-BPY(Pd))and successfully performed a Suzuki-Miyaura cross coupling reaction with various substrates in aqueous media.It was revealed that each tetrahedral cage of MOP-BPY(Pd)has 4.5 Pd atoms on average and retained its high degree of dispersion up to 3 months in water.The coupling efficiencies of the Suzuki-Miyaura cross coupling reaction exhibited more than 90.0%for various substrates we have tested in the aqueous media,which is superior to those of the molecular Pd complex and metal-organic framework(MOF)anchoring Pd atoms.Moreover,MOP-BPY(Pd)was successfully recovered and recycled without performance degradation.

Double Position Servo Synchronous Drive System Based on Cross-Coupling Integrated Feedforward Control for Broacher

Synchronization errors directly deteriorate the machining accuracy of metal parts and the existed method cannot keep high synchronization precision because of external disturbances. A new double position servo synchronous driving scheme based on semi-closed-loop cross- coupling integrated feedforward control is proposed. The scheme comprises a position error cross-coupling feedfor-ward control and a load torque identification with feed- forward control. A digital integrated simulation system for the dual servo synchronous drive system is established. Using a 20 t servo broacher, performance analysis of the scheme is conducted based on this simulation system and the simulation results show that systems with traditional parallel or single control have problems when the work- table works with an unbalanced load. However, the system with proposed scheme shows good synchronous perfor- mance and positional accuracy. Broaching tests are performed and the experimental results show that the maximum dual axis synchronization error of the system is only 8μm during acceleration and deceleration processes and the error between the actual running position and the given position is almost zero. A double position servo synchronous driving scheme is presented based on crosscoupled integrated feedforward compensation control, which can improve the synchronization precision.

Efficient N-heterocyclic carbene nickel pincer complexes catalyzed cross coupling of benzylic ammonium salts with boronic acids

Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive（hetero）aryl benzylic ammonium salts with（hetero）aryl and alkenyl boronic acids under mild reaction conditions.Even at 2 mol% catalyst loading,a wide range of substrates for both coupling partners with different steric and electronic properties were well tolerated.

ANALYSIS OF COUPLING INFLUENCES OF LABYRINTH SEAL PARAMETERS ON CROSS COUPLED STIFFNESS AND DIRECT DAMPING COEFFICIENT

Labyrinth seal can cause steam-exciting, the structural and operating parameters of labyrinth seal have effect on stability of rotor-system. For investigating the coupling influences of the structure and operating parameters of labyrinth seals on dynamic coefficients, a model of calculating dynamic coefficients of labyrinth seals is presented using a two control volume model. The coupling influences of parameters on cross-coupled stiffness and direct damping of labyrinth seal are discussed. In the conclusion, a reference of preventing steam-exciting vibration and optimum determination of design parameters of labyrinth seals are provided.

Unveiling inverse vulcanized polymers as metal-free,visible-light-driven photocatalysts for cross-coupling reactions

Inverse vulcanized polymers(IVPs) that generated from elemental sulfur and smaller amounts of alkenes have found broad promising applications such as cathode materials for Li-S batteries, dynamic and repairable materials, optics applications, and metal sorption. However, their exploration in organic synthesis is still unprecedented. Here we first report the application of inverse vulcanized polymers in catalysis for organic transformations. A biomass-derived inverse vulcanized polymer(IVP-EAE) is found to be capable of catalyzing cross-coupling reactions in a transition-metal-free fashion under visible light.This method allows the direct C–H functionalization of pyrroles and N-arylacrylamides with(hetero)aryl halides, respectively, leading to the formation of two sets of structurally important scaffolds including pyrrole-containing biaryls and 3,3-disubstituted oxindoles with high selectivity. We anticipate this study will not only unveil the new potential of IVPs, but also offer a distinct type of catalysts for organic transformations.

The Influence of Convergence Movement on Turbulent Transportation in the Atmospheric Boundary Layer

Classical turbulent K closure theory of the atmospheric boundary layer assumes that the vertical turbulent transport flux of any macroscopic quantity is equivalent to that quantity's vertical gradient transport flux. But a cross coupling between the thermodynamic processes and the dynamic processes in the atmospheric system is demonstrated based on the Curier-Prigogine principle of cross coupling of linear thermodynamics. The vertical turbulent transportation of energy and substance in the atmospheric boundary layer is related not only to their macroscopic gradient but also to the convergence and the divergence movement. The transportation of the convergence or divergence movement is important for the atmospheric boundary layer of the heterogeneous underlying surface and the convection boundary layer. Based on this, the turbulent transportation in the atmospheric boundary layer, the energy budget of the heterogeneous underlying surface and the convection boundary layer, and the boundary layer parameterization of land surface processes over the heterogeneous underlying surface are studied. This research offers clues not only for establishing the atmospheric boundary layer theory about the heterogeneous underlying surface, but also for overcoming the difficulties encountered recently in the application of the atmospheric boundary layer theory.

CuI/Proline-catalyzed N-Arylation of Nitrogen Heterocycles

Ma＇s CuI/proline procedure for the catalytic cross coupling between nitrogen heterocycles and aryl halides was markedly improved. The key finding was that K3PO4 was a much better base than K2CO3 for the reaction. With this new reaction condition the cross coupling with aryl iodides could be accomplished in 1,4-dioxane instead of DMSO. This reactin also could be carried out in DMF. Furthermore, the coupling yields under the new conditions are usually higher than in Ma＇s original methods.

Synthesis of α-Arylated Esters from Aryl Halides

An operationally simple and inexpensive catalyst system was developed for the cross coupling of aryl iodides and bromides with ethyl acetoacetate by using CuI as catalyst and Nmethyl glycine as ligand. The reaction represents a novel Cu-catalyzed C-C cross coupling reaction. This procedure is applicable to the preparation of pharmaceutically important α- arylalkanoic acids.

Cu-catalyzed arylation of phosphinic amide facilitated by (±)-trans-cyclohexane-1,2-diamine

Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-trans-cyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for synthesizing arylated phosphinic amides. Both kinetic measurement and theoretical calculation indicated that phosphinic amides were much less reactive than amides by about 10 times in Cu-catalyzed cross coupling.

Copper-mediated synthesis of N,N'-diarylhydrazines from boronic acids

N,N＇-Diarylhydrazines have been prepared via the reaction of N-Boc-aryl hydrazines with boronic acids mediated by copper acetate. This mild reaction condition tolerates the presence of a variety of functional groups.

Modeling and Simulation of Two Axes Gimbal Using Fuzzy Control

The application of the guided missile seeker is to provide stability to the sensor’s line of sight toward a target by isolating it from the missile motion and vibration.The main objective of this paper is not only to present the physical modeling of two axes gimbal system but also to improve its performance through using fuzzy logic controlling approach.The paper is started by deriving the mathematical model for gimbals motion using Newton’s second law,followed by designing the mechanical parts of model using SOLIDWORKS and converted to xml file to connect dc motors and sensors using MATLAB/SimMechanics.Then,a Mamdani-type fuzzy and a Proportional-Integral-Derivative(PID)controllers were designed using MATLAB software.The performance of both controllers was evaluated and tested for different types of input shapes.The simulation results showed that self-tuning fuzzy controller provides better performance,since no overshoot,small steady-state error and small settling time compared to PID controller.

Efficient C-S Cross-Coupling of Thiols with Aryl Iodides Catalyzed by Cu(OAc)_(2)·H_(2)O and 2,2'-Biimidazole

The classical Ullmann C-S cross coupling reaction of aryl iodides with aromatic/alkyl thiols under catalysis of 15 mol%Cu(OAc)_(2)·H_(2)O and 15 mol%2,2'-biimidazole works at 80℃in DMSO for 3 h to provide a variety of aryl sulfides in good to excellent yields.

Cross-Coupling of Aryl Iodides with Malononitrile Catalyzed by Palladium N-Heterocyclic Carbene Complex System

Eight N heterocyclic carbenes (NHC), generated in situ from their imidazolium salts, as ligands of palladium complexes were used for the catalytic coupling of iodobenzene with malononitrile anion. It was found that 1,3 bis(2,4,6 trimethylphenyl) imidazolium chloride (IMesHCl) Pd 2(dba) 3 catalytic system has the highest activity to obtain phenyl malononitrile among the imidazolium salts. The substituted iodoarenes reacted with malononitrile anions by using the catalytic system to give cross coupling products in yields from 50% to 96%.

Domino Cross Dehydrogenative Coupling of 2-Aryl Acetals with Ketones Using DDQ as Oxidant and Reactant Precursor

A novel domino cross dehydrogenative coupling of 2-aryl acetals with unmodified ketones has been developed, using DDQ as both the oxidant and reactant precursor.

Nickel-catalyzed C-N crossing coupling reaction: The synthetic method for N-aryl substituted indenoindole

A nickel-based catalyst was employed for the first time in the crossing-coupling of indenoindoles with bromo-/iodoarenes. A simple and practical method was provided for the synthesis of N-aryl substituted indenoindole and the mechanism of this reaction was discussed.

A Theoretical Insight into the Mechanism of Cu（I）-Catalyzed C--N Coupling between Aryl Halides and Aqueous Ammonia

Computational investigations of Cu（I）-catalyzed C--N coupling between aryl halides and aqueous ammonia without addition of any base or ligand were reported. Density functional theory calculations were performed to re- veal the mechanism of the ligand-free amination reaction for the preparation of primary aromatic amines. Through systematic evaluation of the relative concentrations of possible Cu species in solution, we propose that the active catalyst is the neutral Cu（I） complexes rather than the Cu（I） cations; oxidative addition of aryl bromide is a facile step of the catalytic cycle; reactant （NH3） and solvent molecule （NMP） can act as ligands of Cu species to help re- duce the activation energy of the forward reaction and increase the activation energy of the reverse reaction; except for Pathway B, the deprotonation step is irreversible due to the extreme exothermic feature; the elimination of H20 is kinetically favored, while that of HBr is thermodynamically preferred. These findings should be valuable for the mechanism understandings of the ligand-free Cu-catalyzed C--N cross-coupling reactions and for the further de- velopment of highly efficient amination catalyst systems.

Heterogeneous h-BN@Cyclodextrin@Pd（II） Nanomaterial： Fabrication, Characterization and Application as a Highly Efficient and Recyclable Catalyst for C-C Coupling Reactions

An efficient and ligand-free method for the Suzuki and Heck cross-coupling reactions has been success- fully developed using h-BN-supported palladium as the catalyst. This green methodology represents a cost-effective and operationally convenient process for the synthesis of biaryls, stilbenes and acrylates. Wide scope of substrates, good to excellent yields, low reaction time, water as solvent, ligand-free, non-toxicity and recyclability of the catalyst are the main merits of these protocols. In addition, the h-BN@y-CD@Pd（II） nanomaterial has been fully characte- rized by TG, SEM, IR, XRD, XPS and ICP-AES analysis. And it could be easily recovered and reused for at least nine times without any considerable loss of catalytic activity. Above all, this work demonstrates the possibility of using cyclodextrin-modified h-BN as an efficient support for the hydrophilic heterogeneous catalysts.

Oxidative intramolecular coupling of 2,3-disubstituted phenyl acrylic acids and derivatives promoted by di-tert-butylperoxide

Polymethoxy-substituted phenanthrene-9-carboxylic acids or their methylate are key intermediates for the synthesis of tylophora alkaloids and their analogs. An intramolecular oxidative coupling reaction of unfunctionalized 2,3-disubstituted phenyl acrylic acids and derivatives promoted by di-tert-butylper- oxide gave above intermediates in high yields. The mild reaction conditions and easy purification procedures of this method provide a new approach for the synthesis of phenanthrenes.