Optimization of cross-coupling reaction for synthesis of antitumor drug vismodegib

In order to improve the yield and reduce the cost in the synthesis of antitumor drug vismodegib the key intermediates are prepared and the Negishi reaction step is examined.The effects of different molar ratios of reactants dosages of catalyst and time for refluxing are investigated by using single factor tests.The results demonstrate that when the molar ratios of 2-bromopyridine 2-chloro-N-4-chloro-3-iodophenyl -4-methylsulfonyl benzamide zinc chloride n-butyllithium and tetrakis triphenyl phosphine palladium are changed to 1.0∶0.5∶1.5∶1.1∶0.05 and the mixture is refluxed for 24 h the production yield is improved to 72%.This reaction condition significantly enhances the synthetic efficiency avoids consuming excessive raw materials/catalysts and meanwhile prevents a prolonged reaction time.The optimization of the proportion of reactants and the heating time is proved to be important for the efficiency and economy in cross-coupling reaction to synthesize vismodegib.

Cu(OAc)_2 catalyzed Sonogashira cross-coupling reaction in amines

A simple Cu（OAc）2 catalyzed Sonogashira coupling protocol is presented. It was found that the couplings of a variety of aryl halides with terminal alkynes were conducted smoothly to afford the corresponding desired products in moderate to excellent yields, using Cu（OAc）2 as the catalyst and Et3N as the solvent.

Synthesis of Enamines via the Cross-coupling of Thioamides and Diarylketones Promoted by the Sm/SmI_(2)Mixed Reagent

Enamines, promoted by the samarium/samarium diiodide mixed reagent, were synthesized via the cross-coupling of thioamides and diarylketones in good yields.

Microwave-assisted Palladium Catalyzed Cross-coupling Reaction of Sodium Tetraphenylborate with Carboxylic Anhydrides

A rapid and efficient method for synthesis of unsymmetrical ketones under microwave irradiation is reported.

Highly active and stable supported Pd catalysts on ionic liquidfunctionalized SBA-15 for Suzuki–Miyaura cross-coupling and transfer hydrogenation reactions

Highly dispersed palladium nanoparticles were synthesized in the presence of immobilized ionic liquid on mesoporous silica SBA-15.PdNPs(2.4 nm)_me-Im@SBA-15 catalyst was prepared by the reduction using NaBH_4 as the reducing agent with controlled feed rate and has been investigated as ligand-free catalyst for Suzuki–Miyaura cross-coupling reaction at room temperature in aqueous solution under air.PdNPs catalyst was also prepared in situ from PdCl4_me-Im@SBA-15 during the reaction and demonstrated high activity and stability towards nitrobenzene hydrogenation at high temperature. Both catalysts were reusable at least for four recycle processes without significant loss in activity with simple procedure. The catalysts were characterized by TEM, EXAFS, FTIR and XPS.

Polybinaphthyls of (R)-3,3′-Diiodo-2,2′-binaphtho-20-crown-6 with p-Divinylbenzene via Heck Cross-coupling Reaction

The present paper deals with the polymerization of ( R ) 3,3′ diiodo 2,2′ binaphtho 20 crown 6 with \{ p divinylbenzene\} under Heck coupling reaction condition. Both the monomers and the polymer were analyzed by NMR, FTIR, UV, CD, fluorescent spectroscopy, polarimetry, GPC and elemental analysis. The polymer can emit a strong blue fluorescence and is expected to have the potential application in the polarized blue light emitting sensors. The chiral conjugated polymer exhibits a strong Cotton effect in its Circular Dichroism(CD ) spectrum, indicating the high rigidity of the polymer backbone.

Cu-catalyzed cross-couplings under ligandless conditions

The possibility to carry out Cu-catalyzed cross-couplings under ligandless conditions was studied. It was found that by using K3PO4 as the base, the cross-coupling could proceed successfully between aryl iodides and several types of nucleophiles. Aryl bromides were completely inactive under the same reaction conditions.

Cross-Coupling Correction for LaCoste ＆ Romberg Airborne Gravimeter

Abstract The cross-coupling corrections for the LaCoste ＆ Romberg airborne gravimeter are computed as a linear combination of 5 so-called cross-coupling monitors. The weight factors （coefficients） determined from marine gravity data by the factory are obviously not optimal for airborne application. These coefficients are recalibrated by minimizing the difference between airborne data and upward continued surface data （external calibration） and by minimizing the errors at line crossings （internal calibration） respectively. An integrating method to recalibrate the above-mentioned coefficients and the beam scale factor simultaneously is also presented. Experimental results show that the systemic errors in the airborne gravity anomalies can be greatly reduced by using any of the recalibrated coefficients. For example, the systemic error is reduced from 4.8 mGal to 1.8 mGal in Datong test.

Stereoselective Synthesis of (E)-1,3-Enynyl Bromides via Pd/Cu-cata-lyzed Cross-coupling Reaction of (Z)-α-Bromovinylstannanes

Z)-á-Bromovinylstannanes undergo the cross-coupling reaction with alkynyl iodides in the presence of Pd(PPh3)4 and CuI in THF at room temperature to afford stereoselectively (E)-1, 3- enynyl bromides in good yields.

LOW-VALENT TITANIUM INDUCED REDUCTIVE CROSS-COUPLING REACTION OF ESTERS WITH DIARYL KETONES

The intermotecular coupling reaction of esters with diarvl ketones induced by titanium tetrachtoride and zinc powder was studied.

LOW-VALENT TITANIUM INDUCED REDUCTIVE CROSS-COUPLING REACTION OF ACYL CHLORIDES WITH DIARYL KETONES

Treatment of acyl chlorides and diaryl ketones with an activated Ti(o)reagent,prepared by reduction of TiCl_4 with Zn powder,effects an intermolecular reductive cross-coupling reaction leading to ketones.

The Electrokinetic Cross-Coupling Coefficient: Two-Scale Homogenization Approach

By the two-scale homogenization approach we justify a two-scale model of ion transport through a layered membrane, with flows being driven by a pressure gradient and an external electrical field. By up-scaling, the electroosmotic flow equations in horizontal thin slits separated by thin solid layers are approximated by a homogenized system of macroscale equations in the form of the Poisson equation for induced vertical electrical field and Onsager's reciprocity relations between global fluxes (hydrodynamic and electric) and forces (horizontal pressure gradient and external electrical field). In addition, the two-scale approach provides macroscopic mobility coefficients in the Onsager relations. On this way, the cross-coupling kinetic coefficient is obtained in a form which does involves the &#950 -potential among the data provided the surface current is negligible.

Pd-Catalyzed Unprecedented Cross-Coupling of Mixed Phenols and Halides for the Synthesis of Aromatic Ethers

Phenolic compounds present in medicinal and edible plants such as flavonoids, chalcones, coumarins, quinones, and phenolic acids. The antioxidant potential of phenolic compounds shows potent activities for cancer prevention and its treatment. From a green chemistry point of view, cascade (tandem) reactions are ideal techniques in organic synthesis for building complex structures. Cascade techniques are sometimes observed in coupling reactions under mild conditions with a tolerance of multifunctional groups. It will be interesting to find a cascade type reaction to synthesize polyphenolic ethers. This research project achieves a new cross-coupling method for establishing polyphenolic ethers from mixed phenols and halides in the presence of palladium catalyst in moderate to good yields.

Evaluation of TlOH Effect for Pd⁰-Mediated Cross-Coupling of Methyl Iodide and Excess Boronic Acid Ester toward Fabrication of [¹¹C]CH₃-Incorporated PET Tracer

The use of thallium(I) hydroxide (TlOH) as a base is known to extremely accelerate the Suzuki-Miyaura cross-coupling reaction using organoboronic acid or organoboronic acid ester as a substrate. Here, we investigated the effects of TlOH by comparing with other conventional bases such as KOH, K2CO3, and CsF for Pd0-mediated rapid cross-coupling reactions between CH3I and organoborane reagents, such as phenyl-, (Z)-4-benzyloxy-2-butenyl-, and benzylboronic acid pinacol esters under the conditions CH3I/borane/Pd0/base (1:40:1:3) in THF/H2O or DMF/H2O for 5 min with an aim to fabricate a PET tracer efficiently. Consequently, however, the use of TlOH was much less efficient than the other bases for the acceleration of cross-coupling reactions. Thus, it was reconfirmed that the milder and non-toxic conditions using K2CO3 or CsF so far developed by our group were most appropriate for the rapid C-methylations.

THE SPIN DELOCALIZATION SUBSTITUENT PARAMETER σ 10. SYNTHESIS OF SUBSTITUTED α, β, β-TRIFLUOROSTYRENES BY THE Pd-CATALYZED CROSS-COUPLING OF TRIFLUOROVINYLZINC BROMIDE WITH ARYL HALIDES

Palladium-catalyzed coupling of trifluorovinylzinc reagent with substituted aryl halides Y-C_6H_4-X (Y=p-NO_2, p-and m-COOMe, p-COOH, p-CONH_2, p- and m-CN; X=Br, I, Cl) provides a synthetic method for α, β, β-trifluorostyrenes(Y-TFS's). A series of previously unavailable Y-TFS's were thus obtained.

A Parametric Study of Mechanical Cross-Coupling in Parallel-Kinematics Piezo-Flexural Nano-Positioning Systems

Piezo-electric nano-positioning stages are being widely used in applications in which precision and accuracy in the order of nano, and high scanning speeds are paramount. This paper presents a Finite Element Analysis (FEA) of the parallel piezo-flexural nano-positioning (PPNP) stages to investigate motion interference between their different axes. Cross-coupling is one of the significant contributors to undesirable runouts in the precision positioning of PPNP actuators. Using ABAQUS/CAE 2018 software, a 3D model of a PPNP stage was developed. The model consists of a central elastic body connected to a fixed frame through four flexural hinges. A cylindrical stack of multiple piezoelectric disks is placed between the moving central body and the fixed frame. Extensive simulations were carried out for three different friction coefficients in the piezoelectric disks’ contact surfaces, different frame materials, and different geometrical configurations of the stage and the hinges. As a result, it was observed that the primary root cause of the mechanical cross-coupling effect could be realized in the combination of the slip and rotation of the piezoelectric disks due to their frictional behavior with the stage moving in the tangential direction, concurrent with changes in the geometry of the stage.

Ultrasonic Activation of Suzuki and Hiyama Cross-Coupling Reactions Catalyzed by Palladium

The coupling reaction of aryl bromide and aryl boronic acid in water/DMF as solvent was studied using a palladium-complex as a catalyst in the presence of ultrasound at room temperature. The effect on the reaction of a base and a solvent was also studied with and without ultrasound and was found to increase the speed of the reaction. In this regard, we propose reaction mechanisms that could explain the results obtained.

The Design and Its Application of Cross-Coupled Controller in X-Y Table

In conventional cross-coupled controller design,the method usually ignored the inherent characteristic of time-vary- ing parameters and model uncertainties in system.In this paper,a cross-coupled controller(CCC)using an H~∞control scheme has been proposed to reduce the contouring error for an X-Y table.Furthermore,the proposed CCC design,which is a typical Multi- Input Multi-Output(MIMO)system with linear time varying(LTV)characteristics,has been verified as being internally stable. The simulations are carried on Matlab simulink to verify the proposed method,and the results showed that the proposed method can reduce the contouring error significantly compared with the conventional one.

DESIGN OF LIGHTWEIGHT PUF CIRCUIT BASED ON SELECTABLE CROSS-COUPLED INVERTERS

By analyzing the principle of process variations, a lightweight Physical Unclonable Function （PUF） circuit based on selectable cross-coupled inverters is proposed in this paper. Firstly, selectable cross-coupled inverters are chosen for two delay paths. Simultaneously, the circuit takes challenge signal to control each delay path. The PUF cell circuit is implemented in Semiconductor Manufacturing International Corporation （SMIC） 65 nm CMOS technology and the layout area is 2.94μm × 1.68μm. Then the 64-bit PUF circuit is achieved with the cascade connection of cell circuits. The simulation results show that the randomness is 49.4% and the reliability is 96.5%. Compared to the other works, this PUF circuit improves the encrypt performance and greatly reduces the area.

Low Noise Phase CMOS Quadrature VCO with Superharmonic Coupling Using Cross-Couple Pair

This paper aims to introduce a quadrature VCO (voltage control oscillator) which applies superharmonic coupling. The presented quadrature VCO is suitable to be used, both with 2 × subharmonic mixers, as well as 4×subharmonic mixers. It would be impossible to avoid the presence of harmonics in CMOS VCO circuits. These harmonics are in general, undesirable signals which tend to accompany the desired fundamental signal. There are common-mode nodes (similar to those in the two source nodes in a cross-coupled VCO) in deferential VCO at which higher-order harmonics are present while the fundamental is absent in essence. We can make use of these second-order harmonics which are present at the common-mode nodes of two VCO in order to implement a quadrature connection between the fundamental outputs. The technique through which this is done is called superharmonic coupling. This CMOS quadrature VCO which applies active superharmonic coupling puts an excellent performance in show, with an output power –0.942 dBm for fundamental and –9.751 dBm for subharmonic, phase noise –107.2 dBc/Hz for fundamental and –114.8 dBc/Hz at a 1MHz offset. All of circuit applied are designed and simulated by ADS, 2008.