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We have described a method for oxidative cross-coupling reactions between N-alkyl anilines and terminal alkynes forming N-aryl-N-methylpropargylamines. Superparamagnetic CuFe2O4 nanoparticles were employed as efficient and robust catalyst. The optimum conditions involved the use of tert-butyl hydroperoxide (TBHP) as oxidant and methylating reagent in dimethylacetamide (DMA) solvent at 140 C. The two-step reaction, methylation and C-C cross-coupling, proceeds efficiently and has high selectivity, and good conversions were achieved in short reaction times. Preliminary mechanistic investigation was conducted. The CuFe2O4 nanoparticles could be facilely separated from the reaction mixture by magnetic decantation and could be reused several times with only a slight decrease in catalytic activity.

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Herein, a new concept for the direct synthesis of carbamoyl fluoride derivatives is disclosed. The developed method makes use of CO2 as an inexpensive and abundant C1 source; a variety of amines were successfully converted in the presence of a deoxyfluorinating reagent. The corresponding products were often obtained in excellent yields under mild reaction conditions (1 atm and room temperature). The reaction was easily scaled up, demonstrating the efficiency of the developed process.

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Alzheimer?s disease (AD) is the most common form of age-related neurodegeneration occurs because of deposition of proteins in the form of extracellular plaques containing aggregated amyloid beta (Abeta) peptide and intracellular neurofibrillary tangles composed of aggregated microtubule-binding protein tau. Amyloid aggregation process can be enhanced by several familial AD-associated mutations in Abeta peptide. In this study, we have unravelled the interactions of 40 small molecule inhibitors with the Osaka-mutant of Abeta1?40 peptide at atomic level and characterized modes of their binding to mutant Abeta by docking approaches. We have also compared docking energies of these inhibitors with Osaka-mutant with those previously determined for the wild-type and Iowa-mutant peptides and discussed in light of the peptide conformations and non-covalent interactions. We have also discussed inhibition mechanisms of these three peptides. Our analyses revealed that these small molecules can efficiently inhibit Osaka-mutant. The binding modes of drugs with these three peptides are markedly different and so are the mechanisms of inhibition of these three peptides. Overall analysis of the data reveals that binding energy of Iowa-mutant drug complex is lowest and most stable which is followed wild-type peptide-drug complex followed by Osaka-mutant drug complex. Communicated by Ramaswamy H. Sarma.

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The effective catalytic N-methylation of anilines using CO2 as C1 source and molecular hydrogen as reducing agent was demonstrated using the well-defined [Ru(triphos)(tmm)] catalyst. Secondary and primary (shown) aromatic amines were mono- or dialkylated, respectively, in high yields. N-methylation of amides coupled with the amide hydrogenation offers an efficient approach to unsymmetrical tertiary methyl/alkyl/aromatic amines. Copyright

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The 4′-substituted N-methylbenzenesulfenanilides 1a-c react with Lewis acids, including BF3, AlCl3 and GaCl3, to afford the radical cation intermediates 9a-c, some of which could be detected by e.p.r. spectroscopy.Thus, the 4′-methoxy substituted compound 1a gave the fairly persistent radical cation 9a.In contrast, the radical cation 9b, derived from the 4′-nitro substituted compound 4b, was not detected apparently because it decayed too rapidly forming the very stable radical cation 11b, intermediate in the formation of the rearranged sulfide 10b.The radical intermediates 9a-c react with cyclohexene to give the 1,2-adducts 4a-c, 5 and 6 which are believed to be formed from either the thiiranium ion 7b or the sulfurane 8a,c.

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Seven new chelated cyclometalated Ir complexes of ABON,P, ABON,O, and ABON,C(carbene) based on a rigid and tunable 2-arylbenzo[d]oxazole backbone have been prepared for the N-methylation of amines. Among these three coordinated modes, ABON,C(carbene)-chelated iridium-based catalysts exhibited good performance in the monomethylation of aromatic amines with methanol (MeOH) as the green methylation reagent. The steric-modified synthesis of ABON,C(carbene) complexes was described. The most active ABON,C(carbene) complex with marginal steric hindrance as a catalyst was obtained from the benzoxazole ring without a substituent and methyl group of the benzimidazole ring on the N-heterocyclic carbene (NHC) ligand. A variety of amines including para- and meta-substituted aromatic amines, as well as heterocyclic amines, were formulated as suitable substrates. Importantly, this catalyst considerably promoted the yield of the N-methylation of ortho-substituted aromatic amines. Controlled kinetic experiments and deuterium-labeling reactions of these ortho-substituted amines were conducted under optimized conditions. On the basis of the experimental results, a plausible mechanism was proposed.

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The electronic and molecular structures of 9,10-diamino-substituted anthracenes with different N-substituents have been re-examined. In particular, different N-substituents influence both the electronic and molecular structures of the oxidized species of 9,10-diaminoanthracenes. The anthrylene moiety of 9,10-bis(N,N-di(p-anisyl)amino)anthracene retains its planarity during the course of two successive one-electron oxidations, whereas 9,10-bis(N,N-dimethylamino)anthracene and 9,10-bis(N-p-anisyl-N-methylamino)anthracene undergo a substantial structural change to a butterfly-like structure through a two-electron oxidation process. The structural changes observed for the oxidized states are ascribed to significant differences in the frontier molecular orbitals of the above-mentioned three kinds of 9,10-diaminoanthracenes due to different extents of mixing between the amine-localized and anthrylene-localized orbitals.

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We developed an environmentally friendly iridium-catalyzed direct cyclization of aromatic amines with diols that generates the corresponding N-heterocyclic compounds with water as the sole by-product. Thus, under conditions of 165 C for 18 hours, the direct cyclization of N -methylanilines with 1,3-propanediol by using an IrCl 3 catalyst with rac -BINAP as a ligand in mesitylene afforded the corresponding tetrahydroquinoline derivatives with yields ranging from 73 to 83%. Under similar reaction conditions, direct cyclization of anilines with 1,3-propanediol produced the corresponding tetrahydrobenzoquinolizine derivatives with yields ranging from 26 to 76%.

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Diethylenetriamine is effective for the direct cleavage of unactivated carbamates and ureas without additional reagents and catalysts. Various carbamates and ureas were cleaved to afford products in good yield, and the reactions were not affected by air or moisture. Unique chemoselective cleavage of carbamate and urea in the presence of amides was also achieved.

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A manganese-catalyzed one-pot conversion of nitroarenes into N-methylarylamines has been developed. This transfer hydrogenation method employs a well-defined bench stable Mn PN3P pincer precatalyst in combination with methanol as both the reductant and the C1 source. A selection of commercially available nitroarenes was converted into N-methylarylamines in synthetically useful yields.

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