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N-Aryl-N-methylaminocyclohexanols 10-12 were synthesised and their crystal structures were studied by X-ray diffraction. Compound 10 crystallizes in the monoclinic space group Cc with cell parameters of a = 13.7366(2) A, b = 13.7234(2) A, c = 26.9057(5) A, beta = 93.0900(5), V = 5064.70(14) A3 and Z = 16. Compound 11 crystallizes in the trigonal space group P 3 with cell parameters of a = b = 25.4429(4) A, c = 9.6417(2) A, V = 5405.27(16) A3 and Z = 18. Compound 12 crystallizes in the monoclinic space group P21/n with cell parameters of a = 9.9511(2) A, b = 11.5777(2) A, c = 20.5968(4) A, beta = 95.5037(9), V = 2362.04(8) A3 and Z = 8. All three structures were characterised by arrays of hydrogen bonding interactions and these crystallographic studies revealed conformations of 10-12 which gave valuable information into the mechanism of the reaction during their formation. Graphical Abstract: Crystals of (RS,RS,RS)-3-[N-methyl-N-(4′-methoxyphenyl) amino]cyclohexane-1,2-diol, (RS,RS,RS)-3-(N-methyl-N-phenylamino)cyclohexane-1, 2-diol and (RS,RS,RS)-2-fluoro-6-(N-methyl-N-phenylamino)cyclohexan-1-ol were synthesised and their structures were studied by X-ray diffraction.[Figure not available: see fulltext.].

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Racemic pyrrolo [2,3-b]indoles were efficiently synthesized by the reaction of aromatic hydrazines with 4-chloro-2-methylbutanal. A formal total synthesis of physostigmine was achieved.

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The present invention relates to a process for preparing diaryl-substituted isoxazole using compounds of Formula (V) and Formula (VII): where Y is and to processes for preparing valdecoxib and parecoxib.

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In the presence of a Na-exchanged Y faujasite, the reaction of primary aromatic amines 1 with 2-(2-methoxyethoxy)methylethyl carbonate [MeO(CH2)2O(CH2)2 OCO2Me, 2a] yields the corresponding mono-N-methyl derivatives ArNHMe with selectivity up to 95%, at substantially quantitative conversions. At 130C, the reaction can be run under diffusion-free conditions and is strongly affected by the solvent polarity: for instance, in going from xylene (epsilonr = 2.40) to triglyme (epsilonr = 7.62) as the solvent, the pseudo-first-order rate constant for the aniline (1a) disappearance shows a 5-fold decrease. In DMF (epsilonr = 38.25), the same reaction does not occur at all. Competitive adsorption of the solvent and the substrate onto the catalytic sites accounts for this result. The behavior of alkyl-substituted anilines ZC6H4NH2 [Z = p-Me, p-Et, p-Pr, p-(n-Bu) (1b-e); Z = 3,5-di-tert-butyl- and 2,4,6-tri-tert-butylanilines (1f,g)] and p-alkoxyanilines p-ZC6H4NH2 [Z = OMe, OEt, OPr, O-n-Bu (1b?-e?)] clearly indicates a steric effect of ring substituents: as diffusion of the amine into the catalytic pores is hindered, the reaction hardly proceeds and the mono-N-methyl selectivity (SM/D) drops as well. Moreover, the strength of adsorption of the amine onto the catalyst influences the rate and the selectivity as well: the reaction of p-anisidine and p-toluidine – despite the higher nucleophilicity of these compounds – is slower and even less selective with respect to aniline. From a mechanistic viewpoint, the intermediacy of carbamates ArN(Me)CO2R [R = MeO-(CH2)2O(CH2)2] is suggested. At 90C, the reaction of benzylamine (7) – a model for aliphatic amineswith dimethyl carbonate shows that the reaction outcome can be improved by tuning the amphoteric properties of the catalyst: in going from CsY to the more acidic LiY zeolite, methylation is not only more selective (SM/D ratio increases from 77% to 84%) but even much faster (CsY, conversion of 36% after 22 h; LiY, conversion of 43% after 7 h).

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Unique self-assembled macrocyclic multinuclear ZnII and NiII complexes with binaphthyl-bipyridyl ligands (L) were synthesized. X-ray analysis revealed that these complexes consisted of an outer ring (Zn3L3 or Ni3L3) and an inner core (Zn2 or Ni). In the ZnII complex, the inner Zn2 part rotated rapidly inside the outer ring in solution on an NMR timescale. These complexes exhibited dual catalytic activities for CO2 fixations: synthesis of cyclic carbonates from epoxides and CO2 and temperature-switched N-formylation/N-methylation of amines with CO2 and hydrosilane.

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The C-C bond-forming catalytic hydroaminoalkylation of terminal alkenes or styrenes enables a direct and 100 % atom-efficient synthesis of amines and can generally result in the formation of two regioisomers, the branched and the linear product. Herein, we report that high-yielding intermolecular hydroaminoalkylation reactions of styrenes can be achieved with excellent regioselectivities in the presence of the commercially available homoleptic catalyst pentakis(dimethylamino)tantalum. In all cases, the branched regioisomer is formed almost exclusively. Highly regioselective intermolecular hydroaminoalkylation reactions of styrenes are achieved in the presence of the commercially available homoleptic catalyst [Ta(NMe2)5]. The process activates the alpha-C-H bonds of N-methylanilines and 1,2,3,4-tetrahydroquinoline and gives access to the corresponding branched hydroaminoalkylation products in good-to-excellent yields. Copyright

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The present invention provides compounds of Formula (I), or stereoisomers, tautomers, or pharmaceutically acceptable salts or solvates thereof, wherein all the variables are as defined herein. These compounds modulate the activity of farnesoid X receptor (FXR), for example, as agonists. This invention also relates to pharmaceutical compositions comprising these compounds and methods of treating a disease, disorder, or condition associated with FXR dysregulation, such as pathological fibrosis, transplant rejection, cancer, osteoporosis, and inflammatory disorders, by using the compounds and pharmaceutical compositions.

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Various novel 10-alkyl-2-deoxo-2-methylthio-5-deazaflavins have been synthesized by reaction of 6-(N-alkylanilino)-2-methylthiopyrimidin-4(3H)-ones with Vilsmeier reagent. The similar 2-(N-substituted amino) derivatives were prepared by nucleophilic replacement reaction of the 2-methylthio moiety by appropriate amines. The 2-oxo derivatives (i.e., 5-deazaflavins) were obtained by acidic hydrolysis of the 2-methylthio derivatives. The antitumor activities against CCRF-HSB-2 and KB cells and the antiviral activities against HSV-1 and HSV-2 have been investigated in vitro, and many compounds showed promising antitumor activities. Furthermore, AutoDock molecular docking into PTK has been done for lead optimization of these compounds as potential PTK inhibitors. Whereas, the designed 2-deoxo-5-deazaflavins connected with amino acids at the 2-position exhibited the good binding affinities into PTK with more hydrogen bonds.

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The design of an easy to use catalyst system for the regio- and diastereoselective intermolecular hydroaminoalkylation of alkenes with secondary amines is reported. The method utilizes commercially available ligands and tantalum starting materials, and does not require the isolation of air and water sensitive organometallic complexes. The in situ prepared catalyst is active toward a variety of secondary amine substrates, including those with ethyl substituents which yield alpha- and beta-alkylated amines as a single diastereomer. This catalytic transformation can be used to prepare amines containing functionality that promotes ring closure to achieve the diastereoselective synthesis of di- and trialkylated N-heterocycles.

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An active Pd/ZrCuOx catalyst was prepared for the reductive amination of CO2. The N-methylation of amines and nitro compounds with CO2/H2 can be realized with up to 97% yield under relatively mild reaction conditions. N-Formylation becomes the main reaction if the reaction was performed under milder conditions or using Pd/ZnZrOx as the catalyst.

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