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(Figure Presented) No preactivation of the alcohol substrates is required in allylic, propargylic, and benzylic aminations catalyzed by a combination of commercially available Bi(OTf)3 and KPF6, mostly at room temperature (see scheme). The substitution reactions of readily accessible allylic, propargylic, and benzylic alcohols with sulfonamides, carbamates, and carboxamides give the desired amine products in up to 99% yield.

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(Chemical Equation Presented) Immobilization of copper onto modified Wang resin provided a polymer-supported copper catalyst, which is effective in cross-coupling reactions between N- or O-containing substrates and arylboronic acids. The copper catalyst is air stable and can be recycled with minimal loss of activity.

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N-Acylethanolamine-hydrolyzing acid amidase (NAAA) is a lysosomal enzyme that catalyzes the hydrolysis of endogenous fatty acid ethanolamides (FAEs), such as N-palmitoylethanolamide (PEA). PEA exhibits anti-inflammatory and analgesic activities by engaging peroxisome proliferator-activated receptor alpha (PPAR-alpha). Preventing PEA degradation by inhibition of NAAA has been proposed as a novel strategy for the treatment of inflammation and pain. In the present study, we reported the discovery of the oxazolidone derivative as a novel scaffold for NAAA inhibitors, and studied the structure-activity relationship (SAR) by modification of the side chain and terminal lipophilic substituents. The results showed that the link chain length of C5, straight and saturated linkages were the preferred shape patterns for NAAA inhibition. Several nanomolar NAAA inhibitors were described, including 2f, 3h, 3i and 3j with IC50 values of 270 nM, 150 nM, 100 nM and 190 nM, respectively. Enzymatic degradation studies suggested that 2f inhibited NAAA in a selective, noncompetitive and reversible pattern. Moreover, 2f showed high anti-inflammatory and analgesic activities after systemic and oral administration.

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We have evaluated various achiral templates (1a-g, 10, and 16) in conjunction with chiral Lewis acids in the conjugate addition of nucleophilic radicals to alpha-methacrylates followed by enantioselective H-atom transfer. Of these, a novel naphthosultam template (10) gave high enantioselectivity in the H-atomtransfer reactions with ee’s up to 90%. A chiral Lewis acid derived from MgBr2 and bisoxazoline (2) gave the highest selectivity in the enantioselective hydrogen-atom-transfer reactions. Non-C2 symmetric oxazolines (20-25) have also been examined as ligands, and of these, compound 25 gave optimal results (87% yield and 80% ee). Insights into rotamer control in alpha-substituted acrylates and the critical role of the tetrahedral sulfone moiety in realizing high selectivity are discussed.

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Figure presented A Cu-catalyzed aerobic oxidative amidation of propiolic acids via decarboxylation under air has been developed. Only carbon dioxide is produced as byproduct in this approach. The use of air as oxidant makes this method more useful and easy to handle.

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The 1H and 13C NMR spectra carried out on (where for R = H, X = NH, NMe, NEt, CH2, S, O; for R = Me, X = NMe, CH2; for R = Et, X = NEt) are reported.The comparison of these results with those obtained for the thionic and selonic isologues shows that sulphur and selenium have a greater deshielding effect on the ring than oxygen.The resonance of the carbons not involved in the ? system have been correlated with the ? charges calculated by the DEL RE method.

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A catalyst system formed in situ from bis(2-methallyl)cycloocta-1,5-diene- ruthenium(II) [(cod)Ru(met)2], 1,4-bis(dicyclohexylphosphino)butane (dcypb) and ytterbium(III) triflate hydrate (Yb(OTf)3) was found to catalyze the addition of nitrogen nucleophiles to terminal alkynes under mild conditions to stereoselectively form the Z-enamide or Z-enimide products. Various secondary amides and imides could be added across the triple bond of a range of aliphatic and aromatic alkynes. The new bimetallic catalyst system sets new standards with regard to scope and selectivity for the synthesis of Z-configured anti-Markovnikov enamides.

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The present invention relates to novel benzazepine derivatives having pharmacological activity, processes for their preparation, to compositions containing them and to their use in the treatment of neurological and psychiatric disorders.

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Homophthalic anhydride and cyclic imino ethers react to produce fused isoquinolines 6-9.In the case of 2-ethoxy-2-oxazoline, a second compound whose structure is believed to be spiro compound 10 was also isolated.Spectral data for these type systems are discussed.

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A palladium(II) catalyst system has been identified for aerobic dehydrogenation of substituted cyclohexenes to the corresponding arene derivatives. Use of sodium anthraquinone-2-sulfonate (AMS) as a cocatalyst enhances the product yields. A wide range of functional groups are tolerated in the reactions, and the scope and limitations of the method are described. The catalytic dehydrogenation of cyclohexenes is showcased in an efficient route to a phthalimide-based TRPA1 activity modulator.

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