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New d-arabino-hexopyranosid-3-uloses were synthesized by a simple method from mannopyranoside derivatives. The common skeleton possesses a tunable alkoxy group as steric sensor on carbon 2 of the sugar. The new ketones were employed in the dioxirane-mediated epoxidation of a range of trans- and trisubstituted arylalkenes giving enantiomeric excesses from low to good (30-90%). The effect of the size of the steric sensor on the enantioselectivity was also studied. The least bulky group (methoxy group) enhanced the stereoselectivity (up to 90% ee toward triphenylethylene).

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A step-economical method for synthesis of alpha-CF2H-substituted ketones from readily available alkene feedstocks has been developed. Radical difluoromethylation of aromatic alkenes combining DMSO oxidation and photoredox catalysis is a key to the successful transformation. Electrochemical analysis, laser flash photolysis (LFP), and density functional theory (DFT) calculations reveal that N-tosyl-S-difluoromethyl-S-phenylsulfoximine serves as the best CF2H radical source among analogous sulfone-based CF2H reagents. The present photocatalytic keto-difluoromethylation has been applied to flow synthesis and easily scaled up to gram-scale synthesis within a reasonable reaction time. Furthermore, potentials of the alpha-CF2H-substituted ketones for useful synthetic intermediates are shown; e.g., synthesis of the CF2H-containing alpha-hydroxyamide with the same carbon skeleton as that of the anticonvulsant active CF3-analogue, is disclosed. Additionally, mechanistic studies are also discussed in detail.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A simple procedure was suggested for the chromatographic analyses of bio-oils from pyrolysis of various feedstock employing different technologies. An acetonitrile solution of each bio-oil was prepared without any extraction or other sample pretreatments. Preliminary thin layer chromatography showed a large number of compounds having a broad range of retention factors (Rfs) among 0-1. Products having a retention factor over 0.9 were mainly detected by GC while some other compounds were only identified by HPLC. GC/MS-FID analysis was used to identify and quantify compounds using peak areas and relative response factors (RRFs). A new equation was proposed to estimate RRFs of compounds identified via their MS spectra when experimental RRFs were not readily available. The novel procedure was employed to characterize bio-oils from pyrolysis of wood of different source or obtained using different pyrolysis procedure. Using this RRF method guaiacol, furfural, butan-2-one, levoglucosan, acetic acid and many other compounds were quantified in bio-oil samples. Different amount of them were found as a function of the type of wood, and pyrolysis conditions adopted. For instance levoglucosan was the main compound using carbon as MW absorber however acetic acid was prevalent when a MW absorber was not employed and both of them were absent in bio-oils from classical heating. The HPLC/MS of bio-oils showed cyclohexancarboxylic acid, 1,2,4-trimethoxybenzene and 2,6-dimethylphenol among the main products present in all bio-oils. On the contrary 4-hydroxyacetophenone and (3,4,5-trimethoxy) acetophenone were present in bio-oil from pyrolysis of wood using MW oven and 2,5-furandiylmethanol when a MW oven without any absorber was employed. Cyclohexanone was present in bio-oils obtained with a thermal heating or a MW oven without any absorber.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Pyrolytic behavior and kinetic of wood sawdust were studied at non-isothermal and isothermal conditions. The characteristic temperatures of ?230 C, ?300 C, ?345 C, ?370 C corresponded to degradation of pseudo hemicelluloses 1, hemicellulose 2, cellulose, lignin under non-isothermal condition, respectively. The release behaviors of gaseous products were closely related to the characteristic temperatures of weight loss. The tar generation could be characterized by ?CH3 group that was mainly dominated the by decompositions of hemicelluloses and cellulose. Under isothermal condition, the weight of derived biochar was described by a function of wchar = 775.5?2.9T + 0.0037T2-1.6 × 10?6T3. A novel nth-order discrete distributed activation energy model was developed to study the non-isothermal kinetic. The characteristic weight fractions of woody sawdust pyrolysis were found at conversions of 0.29, 0.30, 0.65, 0.84, 0.88 and 0.95. Parallel reaction model could explain the non-isothermal kinetic well with similar reaction orders to discrete distributed activation energy model. The isothermal kinetic of pyrolysis could be described by three or four components parallel reaction with nth-order Avrami-Erofeev model.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The Fe/ZSM-5 catalyst was prepared and used for fast pyrolysis of biomass to aromatic hydrocarbons by pyrolysis-gas chromatography/mass spectrometry experiments (Py-GC/MS). It was found that the Fe/ZSM-5 catalyst demonstrated better activity in the conversion of oxygenates and formation of monocyclic aromatic hydrocarbons (MAHs) than the ZSM-5 catalyst. Furthermore, for catalytic fast pyrolysis of biomass with Fe/ZSM-5 catalyst, the yields of aromatic hydrocarbons were significantly increased with the rise of temperature from 500 C to 600 C, and then decreased with the increase of temperature from 600 C to 800 C. Based on the results of catalyst characterization and activity experiments, it seems that the Fe/ZSM-5 catalyst maintained the structure of ZSM-5, and the incorporation of Fe into ZSM-5 zeolites contributed to the formation of MAHs and simultaneously hindered the further polymerization reaction of MAHs and other oxygenates.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The (13)C n.m.r. chemical shifts of several 2-substituted indenes are reported and the induced substituent shieldings of the remote proton-bearing aromatic carbons are analysed by a multivariate data analysis method.A dual parameter model is necessary to describe the shift variations and the two components obtained were found to correlate to a mesomeric ?R0 and field-inductive ?1 scale, respectively.The two dual parameter models are tested on a structurally similar heterocyclic system.The limitations of multiparameter equations in predicting (13)C chemical shifts and in separating electronic effects are briefly discussed.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 2177-47-1, molcular formula is C10H10, introducing its new discovery. HPLC of Formula: C10H10

Embodiments of the present disclosure directed towards polymerization catalysts having improved ethylene enchainment and/or improved catalyst productivity. As an example, the present disclosure provides a polymerization catalyst of Formula (I), wherein each of R1 to R12 is independently a C1 to C20 alkyl, aryl or aralkyl group, or a hydrogen, wherein at least one of R4 to R7 is not a hydrogen, wherein M is a Group 4 metal, and wherein, each X is independently a halide, C1 to C20 alkyl, aralkyl or hydrogen

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 2177-47-1, molcular formula is C10H10, introducing its new discovery. Product Details of 2177-47-1

ansa metallocene complexes of Ti, Zr and Hf were synthesized, characterized and tested as catalysts for homogeneous ethylene polymerization. The ligand system comprises two indenyl moieties tethered at the 1,1?-positions via a 2,2?-dimethyl biphenylene bridge. The ligand precursor was obtained by the reduction of diphenic acid using lithium aluminum hydride (LiAlH4), followed by the reaction with phosphorus tribromide, and, finally, the reaction with indenyllithium. The corresponding group (IV) metal complexes were synthesized by deprotonation of the ligand precursors using n-BuLi followed by reactions of the corresponding metal tetrachloride. After activation with methylaluminoxane (MAO), the zirconium and hafnium complexes proved as highly active catalysts for ethylene polymerization. The zirconium complex 6 showed the best performance with 12,460 kg PE/mol cat. h. The titanium complex 5 showed no catalytic activity obviously because of decomposition reactions.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The cyclopropylcarbinyl radical rearrangement has been used to probe the photochemistry and photophysics of S2 and S1 in 2-cyclopropylindene (2CPI) and 3-cyclopropylindene (3CPI). Studies in solution and the gas phase are described. Population of S2 with 254 nm light excitation in the gas phase produces the anticipated ring expansion products 2,3,3a,8- tetrahydrocyclopenta[a]indene (1, Phi1 = 0.1) and 1,3,3a,8- tetrahydrocyclopenta[a]indene (2, Phi2 = 0.06) from 2CPI and 3CPI, respectively (Scheme 3). Direct excitation into the S2 state (254 nm) of 2CPI in solution also produces compound 1. The efficiency of the solution phase chemistry is a function of excitation wavelength (Phi1 = 0.022 and 0.006 for 254 and 280 nm, respectively). The solution phase excitation spectrum of 2CPI shows an anomalous dependency on monitoring wavelength which is attributed to a conformational equilibrium. The S1 singlet lifetimes of the cyclopropylindenes are quite short (0.39 and 1.0 ns for 2CPI and 3CPI, respectively) relative to the previously measured values for the corresponding methylindenes (2.3 and 13.9 ns). These shortened lifetimes are attributed to cyclopropyl ring opening in S1 with rates of 2.1 x 109 and 9.2 x 108 s-1 for 2CPI and 3CPI, respectively. Semiempirical excited state calculations support descriptions of the S2 and S1 states of alkylindenes as biradicals.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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sigma-Methyl-(eta5-indenyl)chromium tricarbonyl (III) rearranges quantitatively into (eta6-1-endo-methylindene)chromium tricarbonyl (IV) in C6D6 solution at 30-60C. Methyl group attachment to the positions 2 or 3 of indenyl ligand in (III) has no influence on the activation parameters of this ricochet inter-ring haptotropic rearrangement (DeltaG# = 23.6 kcal mol-1; DeltaH# = 18.9 ± 0.2 kcal mol-1; DeltaS# = -18.6 ± 0.2 cal K-1 mol-1). (IV) undergoes further irreversible isomerization at 60-120 into (eta6-3-methylindene)chromium tricarbonyl (V) with a higher activation barrier (DeltaG# = 28.5 ± 0.1 kcal mol-1) via two consecutive [1,5]-sigmatropic hydrogen shifts. The mechanisms of both rearrangements have been studied in detail using density functional theory (DFT) calculations with extended basis sets. Calculations show that the rearrangement (III) ? (IV) proceeds in two steps. Methyl group migration from chromium into position 1 of the indenyl ligand is the rate-determining step leading to the formation of the 16-electron intermediate (VII). The calculated activation barrier (Ea = 19.6 kcal mol-1) is in good agreement with the experimental one. Further rearrangement (VII) ? (V) proceeds via a trimethylenemethane-type transition state (XVIII) with an activation barrier 11.8 kcal mol-1. The coordination of the chromium tricarbonyl group at the six-membered ring has only minor influence on the kinetic parameters of the hydrogen [1,5]-sigmatropic shift in indene.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI