Catalytic Organic Synthesis

Phenols can be efficiently reduced by sodium formate and Pd/C as catalyst in water and in the presence of amines to give the corresponding cyclohexylamines. This reaction works at room temperature for 12 h or at 60 °C under microwave dielectric heating for 20 min. With the exception of aniline, primary, secondary amines, amino alcohols and even amino acids can be used as nucleophiles. The reductive process is based on sustainable hydrogen source and a catalyst that can be efficiently recovered and reused. The protocol was developed into a continuous-flow production of cyclohexylamines in gram scale achieving very efficient preliminary results (TON 32.7 and TOF 5.45 h -1 ).

An efficient one-pot four-component strategy involving aldehydes, amines, alkynes and isothiocyanates has been developed to access a novel series of thiazolidine-2-imines (5a-x). This process operates under the action of a cooperative catalysis composed of Cu(I) and Zn(II) delivering the desired five-membered heterocyclic compounds in good to excellent yields. Notably, this transformation avoids the use of pre-formed imines or propargylamines and proceeds via an intramolecular 5-exo-dig hydrothiolation reaction of the in situ formed propargyl thiourea. Furthermore, the biological application of these motifs was demonstrated in terms of their strong acetylcholinesterase (AChE) inhibitory activity where compound 5s was identified as the lead AChE inhibitor with an IC 50 value of 0.0023 ± 0.0002 μM, 88-folds stronger inhibition than standard drug (neostigmine methyl sulphate; IC 50 = 0.203 ± 0.004 μM). Molecular docking analysis reinforced the in vitro biological activity results revealing the formation of several useful interactions of the potent lead with amino acid residues in the active site of the enzyme.

As a method to generate all-carbon molecules having highly reactive polyyne units from stable precursors, the [2 + 2] cycloreversion of [4.3.2]propella-1,3,11-triene derivatives was developed. To test the efficiency of this method, the reaction was first applied to simple diethynyl-and dibutadiynyl-substituted propellatrienes, which produced upon UV-irradiation linear hexatriyne and decapentayne derivatives, respectively. Next, dehydro[12]-, [16]-, [18]-, [20]-, and [24]annulene derivatives annelated by the [4.3.2]propellatriene units were prepared as precursors to the corresponding cyclo[n]carbons, a monocyclic form of carbon clusters. Laser-desorption mass spectra of the dehydroannulenes exhibited, in the negative mode, peaks due to the corresponding cyclo[n]carbon anions (n) 12, 16, 18, 20, and 24) formed by successive losses of aromatic indane fragments. Solution photolysis of the dehydro[16]annulene and dehydro[18]annulene derivatives formed reactive polyyne intermediates by [2 + 2] cycloreversion which were intercepted by furan to give the corresponding Diels-Alder adducts. The structures and spectroscopic properties of the dehydroannulenes annelated by the [4.3.2]propellatriene units, the precursors to cyclo[n]carbons, and those annelated by the oxanorbornadiene units, the products of the photolysis in furan, are discussed.

An efficient one-pot four-component strategy involving aldehydes, amines, alkynes and isothiocyanates has been developed to access a novel series of thiazolidine-2-imines (5a-x). This process operates under the action of a cooperative catalysis composed of Cu(I) and Zn(II) delivering the desired five-membered heterocyclic compounds in good to excellent yields. Notably, this transformation avoids the use of pre-formed imines or propargylamines and proceeds via an intramolecular 5-exo-dig hydrothiolation reaction of the in situ formed propargyl thiourea. Furthermore, the biological application of these motifs was demonstrated in terms of their strong acetylcholinesterase (AChE) inhibitory activity where compound 5s was identified as the lead AChE inhibitor with an IC 50 value of 0.0023 ± 0.0002 μM, 88-folds stronger inhibition than standard drug (neostigmine methyl sulphate; IC 50 = 0.203 ± 0.004 μM). Molecular docking analysis reinforced the in vitro biological activity results revealing the formation of several useful interactions of the potent lead with amino acid residues in the active site of the enzyme.

A series of novel N-alkylcarbazol-propargylamine hybrids were designed and synthesized by Cu I Br-catalyzed A 3-coupling of N-octylcarbazol-3-carbaldehyde, amines, and alkynes. The trisubstituted propargyl amines decorated with carbazole moiety were obtained under solvent-free conditions in good to moderate yields. Furthermore, the scope of the method was studied, which was found to be applicable to primary aliphatic and aromatic amines. Also, a large variety of substituents both on alkynes and anilines are well tolerated.

Solvent-free aminocarbonylation (Heck carbonylation) of aryl halide, catalyzed by µ-dichloro-bis(benzylidene aniline)palladium(II) complex
yields dimethyl benzamide and their substitutes, has several useful industrial applications. In present work, dimethylformamide (DMF)
serves as an effective in situ supplier of dimethyl amine and carbon monoxide. Bromobenzene along with more electron-rich aryl bromide
generally undergo these reactions very smoothly, but the yield of respective products is less. To increase the yields of aryl amide, it is
needed to be add amines from the external sources to the reaction mixture. Imidazole and aniline were used as good reaction partners, or
amines, in this experiment. For obtaining the best results, several reactions were conducted in the presence of base i.e. potassium tertbutoxide. Potassium tert-butoxide was responsible for the better decomposition of DMF and imidazole as an additive. The carbonylation
reactions described here depend on the efficiency of in situ generation of carbon monoxide, which can be a suitable unconventional route
to traditional carbonylation procedures for small-scale operation when a quick reaction time is sought where direct use of CO gas is not
possible.

The present paper highlights the influence of desilication of nanocrystal *BEA zeolites (CP811 and CP814E) by different alkaline treatments in presence of NaOH alone, NaOH + TPABr and NaOH + TBAOH, on the catalytic performance in the hydroisomerization reactions of n-alkanes (n-C 10 , n-C 12 and n-C 14). The well-balanced catalyst was reached after impregnation of 1.5 wt% of Pt, where the activity and isomers selectivity was seen to be the maximum, knowing that the Pt content effect was studied on the CP811 zeolite catalyst. All the other catalysts were after impregnated by approximately 1.5 wt% of Pt. The improvement of the textural properties by means of desilication was not always accounting for the influence of the catalytic performance of the catalysts, but rather it may be the bifunctional characteristics in charge. The impact of chain length was investigated on the catalysts to study if the presence of the inter-and intracrystalline mesopores would account for better diffusion of larger molecules as, n-C 12 and n-C 14. It was found on the majority of the catalysts that the activity was high whether the chain length was, but the isomers selectivity was decreasing with chain length except on one catalyst that possesses high textural and bifunctional characteristics. Among the three n-alkanes studied, n-C 12 have marked the highest TOF values and lowest selectivity to isomers, a phenomenon attributed to the confinement effect that seems to increase the interaction of n-C 12 molecules with the acidic sites of the zeolites, apparently causing their strength to be higher. This effect was pronounced more with n-C 12 than the other two n-alkanes.

High throughput screening of synthetic compounds against vital enzymes is the way forward for the determination of potent enzyme inhibitors. In-vitro high throughput library screening of 258 synthetic compounds (comp. 1–258), was performed against α-glucosidase. The active compounds out of this library were investigated for their mode of inhibition and binding affinities towards α-glucosidase through kinetics as well as molecular docking studies. Out of all the compounds selected for this study, 63 compounds were found active within the IC50 range of 3.2 μM to 50.0 μM. The most potent inhibitor of α-glucosidase out of this library was the derivative of an oxadiazole (comp. 25). It showed the IC50 value of 3.23 ± 0.8 μM. Other highly active compounds were the derivatives of ethyl-thio benzimidazolyl acetohydrazide with IC50 values of 6.1 ± 0.5 μM (comp. 228), 6.84 ± 1.3 μM (comp. 212), 7.34 ± 0.3 μM (comp. 230) and 8.93 ± 1.0 μM (comp. 210). For comparison, the standard (acarbose) sh...

For the first time, a detailed study on the photophysical properties of variously substituted diazoketones and on their photoreactivity under blue LED irradiation was carried out. Despite very limited absorbance in the visible region, we have demonstrated that, independently from their structure, α-diazoketones all undergo a very efficient Wolff rearrangement. Contrarily to the same UV-mediated reaction, where photons can give rise to side processes, in this case, almost all absorbed photons are selective and effective, and the quantum yield is close to 100%. If the rearrangement is carried out in the presence of isocyanides and carboxylic acids/silanols, the photoreactivity is not affected, and the resulting ketenes can afford α-acyloxyand α-silyloxyacrylamides through two distinct multicomponent reactions, performed both in batch and under continuous flow, with improved selectivity and broader scope. These photoinduced multicomponent reactions can be coupled with other visible-light-mediated transformations, thus increasing the diversity of the molecules obtainable by this approach.

An Ugi multicomponent reaction with chiral cyclic amino acids, benzyl isocyanide and cyclic ketones (or acetone) has been exploited as key step for the generation of peptidomimetics. After a straightforward set of elaborations, the peptidomimetics were converted into polycyclic scaffolds displaying two orthogonally protected secondary amines. Libraries of compounds were obtained decorating the molecules through acylation/reductive amination reactions on these functional groups.

A new series of N-acylhydrazone derivatives of 2-mercaptobenzimidazole (2-MBI) has been synthesized through S-alkylation with 1-bromotetradecane and N-alkylation with ethyl-2chloroacetate. The resulting ester was synthetically modified through hydrazine hydrate to acyl hydrazide which was condensed with aromatic aldehydes to afford the title Nacylhydrazones (4-17). Chemical structures of the newly synthesized compounds have been confirmed through mass, FT-IR and 1 HNMR techniques. In vitro free radical scavenging and α-glucosidase inhibition activities of the compounds were investigated with reference to the standard ascorbic acid and acarbose respectively. Amongst the target compounds, 13 showed the highest inhibition in DPPH scavenging assay (IC 50 = 131.50 µM) and α-glucosidase inhibition potential (IC 50 = 352 µg/ml). We extended our investigations to explore the mechanism of enzyme inhibition and conducted docking analysis by using Molecular Operating Environment (MOE 2016.08). A homology model for α-glucosidase was constructed and validated using Ramachandran plot. Docking studies were also carried out on human intestinal α-glucosidases. In view of the importance of the nucleus involved, the synthesized compounds might find extensive medicinal applications as reported in the literature.

Low acidity ZSM-5-supported iron catalysts were synthesized for use in Fischer-Tropsch conversion. Low acidity ZSM-5 was particularly chosen for its lower activity in respect to zeolite-acid catalyzed reactions (i.e. hydrocracking) which might lead to the lower selectivity for the light hydrocarbon and high selectivity for gasoline range components and for its high stability. Selective surface dealumination was also applied to zeolite and the resulting zeolite was used as a support for the catalyst in order to enhance its selectivity for gasoline. Zeolite-supported catalysts were synthesized by using incipient wetness impregnation method and hybrid catalyst was prepared by physical admixing of ZSM-5 and base iron. The performances of catalysts prepared by two different methods were compared with respect to activity, selectivity and hydrocarbon yields. The catalytic activities of the catalysts were found to be considerably affected by the catalyst preparation method, percentage of iron in the catalyst and the reaction temperature. All catalysts displayed a CO conversion higher than 40% at 553 K. The selectivity toward C5-C11 hydrocarbons of catalyst prepared by impregnation method was determined to be 50-74%. The selectivity of the hybrid catalyst toward the same fraction was about 45%. No wax was detected in the products during the FT process using zeolite-supported iron catalysts. About 2 wt.% wax was measured in the FT products obtained by hybrid catalyst under similar conditions. Catalyst prepared with dealuminated zeolite displayed higher gasoline range hydrocarbon selectivity in comparison with catalysts having same iron content. Results of a 260 h time-on-stream test, carried out for one of the supported iron catalysts with 8 wt.% Fe, indicated that the catalyst was stable without any activity loss.

A series of new benzimidazolium chlorides bearing N,N′‐benzyl, 2,4,6‐
trimethylbenzyl and 2,4,6‐triisopropylbenzyl substituents have been designed
and synthesized from various o‐phenylenediamines. Subsequently, corresponding
Cu‐based N‐heterocyclic carbenes (NHCs) were generated in situ in the
reaction medium which represents a new application of NHCs exploiting distinct
catalytic property towards intermolecular cyclization reaction cascade
for the synthesis of 2‐aryl‐3‐(arylethynyl)quinoxalines from ophenylenediamines
and terminal alkynes. The outcome of the cyclization reaction
product depends upon the N,N′‐substituents present on the
benzimidazolium chlorides.

Phase transformation, structural and optical properties of ZnO/CuO composite for various milling times were studied by means of X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy, respectively. The refractive index (n), extinction coefficient (k), dielectric function, energy-loss function (Im(-1/(ε)), and optical absorption coefficient were determined from the quantitative analysis of FTIR spectra by applying Kramers-Kronig relation. Density of states (DOS) was analyzed using Quantum ESPRESSO package. For milling time up to 12 h, crystalline phase is dominant and for >12 h, phase transformation changed from crystalline to amorphous. The crystallite size shows a decrease with increasing the milling time due to Zn and Cu atoms spreading each other and producing the individual crystalline structure. For 20 h milling time, it shows the minimum distance (Δ) between two optical phonon modes due to the enlarging lattice. For various milling time, the density of states (DOS) is similar for each composite due to the crystalline phase (%) for composites also similar. The best degradation percentage is 96.8% and only 30 min irradiation time for sample 1 h milling. For milling 20 h up to 52 h, the degradation decreases from 93.10% to 78.5% and up again to 91.5% for 56 h milling which the trend is opposite with longitudinal optical phonon mode. This study shows powerful method for determining optical properties from FTIR spectra and effective way to investigate the transformation phase and structural properties from XRD spectra of CuO/ZnO composite.

We report the utilization of a novel catalyst for cycloisomerizations. The novel catalyst system contains gold nanoparticles supported on Al-SBA15, which was prepared by the ball-milling process. We developed a greener methodology for synthesizing spiroindolines under heterogeneous conditions, using this novel class of supported gold nanoparticles in combination with microwave irradiation. The catalyst is highly reusable and selective. Cycloisomerization reaction yields ranged from good to excellent leading to the formation of two novel classes of six-and seven-membered heterocycles, which have been unprecedented so far. The selectivity of the catalyst towards the desired products is high and the reaction can be performed in ethanol as the solvent. A one-pot cascade reaction could be established commencing with the Ugi-reaction to ensure diversity. Scheme 1 Obtained products for post-Ugi-cyclization reactions. † Electronic supplementary information (ESI) available: General experimental procedures; XRD, BET, TEM characterization and discussion of the catalyst; 1 H-NMR, 13 C-NMR spectra and HRMS results of the starting materials and products; the X-ray crystal structure of 4n. CCDC 1033069. For ESI and crystallographic data in CIF or other electronic format see

The activity of n-hexane isomerization with 0,8 %kl Pd/HZSM-5 was studied in a micro reactor in the temperature range of 225-325 oC at 0,1 Mpa with the molar ratio H2/ hydrocarbon of 5.92, n-hexane concentration of 9.2 %mol, GHSV 2698 h-1 at atmospheric pressure. The catalyst owned suitable acidity, reasonable reductivity, good metal dispersion, and appropiate balance between metallic and acidic functions. The catalyst had high activity but low stability. The cause of deactivation was examined via a comparison of physico-chemical properties between a fresh catalyst and a used one. There was no metal sintering. The mono-metallic catalyst performed high activity for n-hexane hydro-isomerization but less stable. Deactivation is mainly attributed to coke formation. Catalyst activity and stability were significantly improved with activity of 0,7 MPa compared to that of 0,1 MPa at elevated pressure. The catalyst Pd-Co/HZSM-5 is capable of resisting against coke, thereby exhibiting high st...

A synthesis of fluorinated pyrimidines under mild conditions from amidine hydrochlorides and the recently described potassium 2-cyano-2-fluoroethenolate was developed. A broad substrate scope was tested and mostly excellent yields were obtained. The synthesis of fluorinated aminopyrazoles from the same fluorinated precursor could be demonstrated but proceeded with lower efficiency.

The challenging carbonylation of propargyl alcohol is effectively catalyzed by Pd(OAc) 2 in combination with diphenyl-(6-methyl-pyridin-2-yl)phosphine and methanesulfonic acid. In dichloroethane at 20-50 • C, the reaction affords with almost complete regioselectivity alkyl 2-(hydroxymethyl)acrylates. Turnover frequency numbers (TOF) of up to 450 h −1 can be achieved working at 50 • C, while a maximum turnover number (TON) of about 730 is obtained at 30 • C. The catalyst longevity is limited because the carbonylation product reacts with the phosphorus atom of the ligand to give a quaternary phosphonium salt. This reaction leads to deactivation of the catalyst and eventually to palladium black formation.

PPDock-PortalPatch Dock (http://140.112.135.49/ppdock/) is a web server that focuses on the search of binding site(s) between the proteins and the drug molecules through docking simulations by applying the genetic programming algorithm (GP) and x-score scoring function. The target protein is at first regarded as a rigid body, whereas the drug molecule is allowed to be entirely flexible. As the starting step, one can obtain the coordinates file of the target protein from the PDB server (Protein Data Bank: http://www.rcsb.org/pdb/home/home.do; ".pdb" format) and then convert the coordinates of the drug molecule(s) to ".mol2" format by way of E-BABEL server (http://www.vcclab.org/lab/babel/). These two files will be used as the input files. For the docking results, the drug molecules will remain as .mol2 format and an Excel file consisting of the number of generations calculated with GP, the number of "evolution" trees, the values for score, the values for RMSD and the file names will be generated as the output file. All the results will be sent via e-mail. One can also check the results by visualizing the accomplished docking structures on line in 20 minutes. During the test period, the server has been running for one month and accepted 120 inputs, including both from our group and about 10-15 individuals from outsides. For these trials, upon utilization of the X-Score as the scoring function, our PPDock software has produced an accuracy rate ranging from 66% to 76% in 100 protein-ligand complexes. In addition, a major purpose to add GP into the virtual screen system was to improve the search efficiency of docking. According to our results, the aforementioned trials were indeed faster than through other servers. It is reliable to use this virtual screen system to perform the docking simulations with both high accuracy and efficiency. Our new web service is now webavailable and free for worldwide users in accelerating the development and design of new lead compounds.

We have evaluated the kinetics of the catalytic oxidation of NO to NO 2 using a Pt/alumina catalyst, under conditions relevant to industrial nitric acid production: NO and steam contents up to 5% and 20%, respectively, with temperatures from 250 to 350°C, and pressures up to 4.7 bar. The objective is to replace the current homogeneous oxidation process, which requires cooling of the process gas and a long residence time, with a more intensive heterogeneous oxidation process, allowing the heat of reaction (114 kJ/mol) to be recovered. This may give a 10% improvement in overall heat recovery and, additionally, lead to reduced capital expenditure (CAPEX) and footprint of new build plants. With world production of nitric acid of 60 million tonnes per annum, the transformation from the homogeneous oxidation of NO to a heterogeneous oxidation can lead to significant environmental benefits and cost reduction.

The new synthesized sulfamic acid functionalized catalyst on the basis of calix[4]resorcinarene catalyzed successfully and efficiently the synthesis of 14-aryl-14H-dibenzo[a,j]xanthene derivatives through a one-pot condensation reaction of β-naphthol with various aryl aldehydes under thermal solvent-free conditions. As the major advantages of the present method, solvent-free and mild acidic conditions, catalyst recyclability, easy purification of the products, high yields along with relatively less reaction times can be mentioned. IR spectroscopy, field emission scanning electron microscopy and transmission electron microscopy are some of the spectroscopic methods used to characterize the new synthesized solid support.

Objective: This study was conducted to synthesise some 2-substituted-5-nitro benzimidazole derivatives to evaluate their antioxidant activity. Methods: The titled compounds were synthesised by sodium metabisulfite mediated reaction of 4-nitro-1, 2-phenylenediamine with a number of para-substituted benzaldehydes. The antioxidant activity was evaluated by 2, 2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging method. Results: All the compounds exhibited good antioxidant activity having IC50 Conclusion: Among the synthesised compounds, compounds 3a-c have been found to possess the most prominent antioxidant activity which might be attributed due to the presence of chloro, bromo and fluoro substituents in the molecule. The compounds may act as the future lead(s) for the development of potential antioxidant compounds. values in the range of 3.17 to 7.59 µg/ml while that of standard butylated hydroxytoluene (BHT) was 18.42 µg/ml.

The use of catalytic membranes as microstructured reactors without a separative function has proved effective. High catalytic activity is possible with minimal mass transport resistances if the reactant mixture is pushed to flow through the pores of a membrane that has been impregnated with catalyst. In this study, n-heptane (C7H16) was hydrocracked and hydro-isomerized within a plug-flow zeolitic catalytic membrane-packed bed reactor. The metallic cobalt (Co) precursor at 3 wt.% was loaded onto support mesoporous materials MCM-48 to synthesize heterogeneous catalysis. The prepared MCM-48 was characterized by utilizing characterization techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), Fourier transform infrared (FTIR), nitrogen adsorption–desorption isotherms, and the Brunauer–Emmett–Teller (BET) surface area. The structural and textural characteristics of MCM-48 after encapsulation with Co were also investigated...

A highly diastereoselective 1,4-addition involving Davies' lithium amide is employed as the key reaction to prepare, in five steps from ethyl acetoacetate, an enantiomerically pure keto protected b,b 0-ketoaminoester. This latter was reacted with aldehydes in an intramolecular Mannich process and furnished a direct and stereoselective access to substituted homopipecolates. The validity of this approach was achieved through a new formal asymmetric synthesis of alkaloid (þ)-Calvine.

Multicomponent reactions Multicomponent reactions O 0359 Polyfunctional Compounds Containing the 4,6-Dialkoxy-7-arylthioheptene Moiety as Synthetically Useful Intermediates. The Course of Lewis Acid-Induced Transformations.-A range of title compounds are prepared by sequential reactions of TosSCl with alkenes. In most cases, they are formed as mixtures of diastereomers with low diastereoselectivity. Lewis acid-induced transformations of these adducts are studied. The type of these transformations, leading either to cyclohexane derivatives or to 1,3-dienes, is found to be dependent on the substrate structure and/or reaction conditions. Both the preparation of the adducts and their conversion in the presence of Lewis acids can be performed in a one-pot sequence thus involving three intermolecular and one intramolecular cationic reactions.

The chemicals Pd(OAc) 2 , PPh 3 , MeOH, MePr, B(OH) 3 , salicylic acid and its derivatives, trifluoroacetic, ptoluenesulfonic and MSA were purchased from Aldrich and used as received. The BSA can either be pre-formed or synthesised in-situ in the reaction mixture. Pre-formed BSA was synthesised by refluxing a solution of one mole of B(OH) 3 with two moles of salicylic acid in toluene and removing three moles of water with a Dean Stark apparatus. Separate addition of B(OH) 3 and salicylic acid to the reaction mixture gives rise to the in-situ prepared BSA. PPh 3 was purified prior to use, by recrystallisation from ethanol. C 2 H 4 and high purity grade CO was supplied by Afrox. General Procedure for the Methoxycarbonylation: General autoclave run: a 300 ml magnetic-driven Parr autoclave constructed from Hastelloy was charged under a constant flow of argon by addition of the following reagents in the order that they are mentioned: Pd(OAc) 2 (0.24 mmol,

Background: Aminoisoquinolines are an important class of heterocyclic compounds. These compounds present a wide range of pharmacological properties including antimalaric, anticonvulsant and anti-inflammatory. Although several preparation routes may be found in the literature for the preparation of these compounds, many of these methods present difficulties, including laborious isolation methods, drastic conditions and extended reaction times. Methods: The synthesis of N-substituted 1-alkyl and 1-aryl-3-aminoisoquinolines is developed through the reaction of 2-acylphenylacetonitriles with amines under microwave irradiation conditions. The reactions were performed in ethanol as a solvent without the use of catalyst. In parallel, these reactions were performed under identical conditions of temperature using P 2 O 5 /SiO 2 as a catalyst in different amounts. Results: A series of N-substituted 1-alkyl and 1-aryl-3-aminoisoquinolines were synthesized using microwave irradiation with as high selectivity, short reaction times and without the use of catalyst. The use of P 2 O 5 /SiO 2 as catalyst under microwave irradiation conditions was not effective for these reactions. Conclusion: The results show an efficient method for the synthesis of N-substituted 1-alkyl and 1-aryl-3-aminoisoquinolines by the reaction of 2-acylphenylacetonitriles with amines using microwave irradiation. Some important advantages for this method include a strong decrease in reaction time, a good selectivity, and the absence of catalyst, with simplicity in operation and a benefit to the environment.

PPDock-PortalPatch Dock (http://140.112.135.49/ppdock/) is a web server that focuses on the search of binding site(s) between the proteins and the drug molecules through docking simulations by applying the genetic programming algorithm (GP) and x-score scoring function. The target protein is at first regarded as a rigid body, whereas the drug molecule is allowed to be entirely flexible. As the starting step, one can obtain the coordinates file of the target protein from the PDB server (Protein Data Bank: http://www.rcsb.org/pdb/home/home.do; ".pdb" format) and then convert the coordinates of the drug molecule(s) to ".mol2" format by way of E-BABEL server (http://www.vcclab.org/lab/babel/). These two files will be used as the input files. For the docking results, the drug molecules will remain as .mol2 format and an Excel file consisting of the number of generations calculated with GP, the number of "evolution" trees, the values for score, the values for RMSD and the file names will be generated as the output file. All the results will be sent via e-mail. One can also check the results by visualizing the accomplished docking structures on line in 20 minutes. During the test period, the server has been running for one month and accepted 120 inputs, including both from our group and about 10-15 individuals from outsides. For these trials, upon utilization of the X-Score as the scoring function, our PPDock software has produced an accuracy rate ranging from 66% to 76% in 100 protein-ligand complexes. In addition, a major purpose to add GP into the virtual screen system was to improve the search efficiency of docking. According to our results, the aforementioned trials were indeed faster than through other servers. It is reliable to use this virtual screen system to perform the docking simulations with both high accuracy and efficiency. Our new web service is now webavailable and free for worldwide users in accelerating the development and design of new lead compounds.

The operation of reforming catalysts in a fixed bed reactor undergoes a high level of interaction between the operating parameters and the reaction mechanism. Understanding such an interaction reduces the catalyst deactivation rate. In the present work, three kinds of nanocatalysts (i.e., Pt/HY, Pt-Zn/HY, and Pt-Rh/HY) were synthesized. The catalysts’ performances were evaluated for n-heptane reactions in the fixed bed reactor. The operating conditions applied were the following: 1 bar pressure, WHSV of 4, hydrogen/n-heptane ratio of 4, and the reaction temperatures of 425, 450, 475, 500, and 525 °C. The optimal reaction temperature for all three types of nanocatalysts to produce high-quality isomers and aromatic hydrocarbons was 500 °C. Accordingly, the nanocatalyst Pt-Zn/HY provided the highest catalytic selectivity for the desired hydrocarbons. Moreover, the Pt-Zn/HY-nanocatalyst showed more resistance against catalyst deactivation in comparison with the other two types of nanoca...

An efficient ligand-free protocol has been developed for the amincocarbonylation of aryl iodides with aromatic/aliphatic amines using palladium(II) acetate as a catalyst in water under milder operating conditions. The system tolerated a wide variety of hindered and functionalized aryl iodides/amines and afforded the desired amides in excellent yields at low catalyst concentration.

In this paper, a novel catalyst is introduced based on the immobilization of palladium onto magnetic Fucus Vesiculosus extract (Pd@mFuVe catalyst). For the synthesis of Pd@mFuVe catalyst, Fucus Vesiculosus extract is obtained from the plant source, followed by the synthesis of superparamagnetic iron oxide nanoparticles (SPION) onto the extract. The catalyst is characterized by several methods, including scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), FT-IR spectroscopy, vibrating sample magnetometer (VSM), powder X-ray diffraction analysis (XRD), and inductively coupled plasma (ICP). The activity of Pd@mFuVe catalyst is studied in the synthesis of N-alkyl-2-(4-methyl-1-oxoisoquinolin-2(1H)-yl)-2-phenylacetamides. The products were synthesized in three steps, the synthesis of 2-iodobenzoic acid from 2-aminobenzoic acid, which participated in a multicomponent reaction with allylamine, aldehydes, and isocyanides, followed by a cyclization reaction, catal...

Dithiocarbamate and DBU-promoted amide bond formation under microwave condition has been reported. The versatility of this synthetic protocol has been demonstrated with various carboxylic acids and different dithiocarbamates. The products thus obtained have been characterized by mp, IR, 1 H NMR, and mass spectroscopy.

In fundamental research and drug discovery, there is still a need for effective and straightforward chemical approaches for generating cyclic peptides. The divergent synthesis of cyclic peptides remains a challenge, in particular when cyclization is carried out in the presence of unprotected side chains and a nonpeptidic component within the cycle is needed. Herein, we describe a novel and efficient strategy based on Au(I)-mediated cyclization of unprotected peptides through rapid (30−60 min) amine addition on a propargyl group to generate an imine linkage. Mechanistic insights reveal that the reaction proceeds via regioselective Markovnikov's addition of the amine on the Au(I)activated propargyl. This strategy was successfully applied to prepare efficiently (56−94%) over 35 diverse cyclic peptides having different sequences and lengths. We have also achieved stereoselective reduction of cyclic imines employing chiral ligands. The practicality of our method was extended for the synthesis of cyclic peptides that bind Lys48-linked di-ubiquitin chains with high affinity, leading to apoptosis of cancer cells.

Gram-scale synthesis of uniform nano-particles of palladium supported on gelatin, as a reductant and ligand is described. These particles were prepared under green conditions without addition of any external reducing agent and ligand. No complicated work up process was needed for the isolation of the nano-particles. Full characterization of the supported palladium particles on gelatin was performed by UV-Vis spectra and also by SEM, TEM and AFM images. The amount of palladium particles on gelatin was determined by induced coupled plasma (ICP) analysis and atomic absorption spectroscopy (AAS) to be 0.09 mmol of Pd per gram of the gelatin. The supported nano-particles of palladium on gelatin were applied successfully as the catalyst in Mizoroki-Heck reaction. The reaction was conducted under solvent-free conditions using tri(n-propyl) amine as a base at 140 • C. This system showed high catalytic activity for the reaction of aryl iodides and aryl bromides with n-butyl acrylate and styrene. In the case of the reaction of aryl iodides with n-butyl acrylate, incredible reaction rates were observed which is unique in comparison with the other methods reported in the literature. The catalyst was recovered and recycled for ten consecutive runs. We have also checked the effect of one of the generated base adduct on the reaction rate.

Naghmana Rashid*, Almas Kiran, Zaman Ashraf, Moazzam Hussain Bhatti, Bushra Mirza Hammad Ismail, Muhammad Rafiq and Jerry P. Jasinski Department of Chemistry, Allama Iqbal Open University, H-8 Islamabad. Pakistan. Department of Biochemistry, Faculty of Biological Sciences, Quaid-i-Azam University Islamabad-45320. Pakistan. Department of Biochemistry and Biotechnology (Baghdad-ul-Jadeed Campus), The Islamia University of Bahawalpur 63100, Pakistan. Department of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001. USA. [email protected]*

Recently, methanol has gained increasing attention thanks to the variety of feedstocks suitable for its production and its low environmental impact granting the molecule a key role in future economic roadmaps as in Olah's development model. Nowadays, fossil sources are not the exclusive sources to produce syngas: biogas is a promising alternative, leading to less severe operating conditions and smaller plant scales. The most widespread kinetic models for methanol synthesis, namely, the Graaf and the Vanden Bussche−Froment models, will be proven not to be fully adequate in characterizing these conditions. A robust refit is shown to outperform predictions from conventional models and follow recent trends in process operations. The refitted Graaf model is more flexible on the operating conditions and feed compositions, removing also some infeasible discontinuities present in conventional models. The final result is a more generalized and accurate Graaf's model for methanol synthesis on CZA catalysts.

We demonstrate the novel spiroannulation of exoimines with 1,3-dipoles, for the first time, leading to 3D spirocycles with a secondary amine (NH) in the spiro-ring. The synthetic method described herein allows access to these previously unexplored heterospirocyclic cores that have application in the discovery of functional molecules for medicinal and materials science. This was demonstrated by discovering an unprecedented class of heterospirocycles with antimalarial activity against the human protozoan P. falciparum.

Synthetic zeolite was successfully prepared by hydrothermal treatment. Structural morphologies, compositions, surface area and acidic strength were analysed by Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), BET surface area and temperature programme desorption (TPD). This zeolite utilized for the synthesis of Oleate ester as biodiesel from oleic acid. The features of this procedure are mild reaction conditions, good yield, the operational simplicity at ambient temperature and it can be easily industrialized.