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Trifluoromethyl epoxy ethers 1 and 2 reacted with aromatic amines in hexafluoro-2-propanol at room temperature providing trifluoromethyl indolinols 3 and 4 in excellent isolated yields. 3-Trifluoromethyl indoles 9 and 10 could be prepared by treatment of indolinols with SOCl2.

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By exploring a new mode of nickel-catalyzed cross-coupling, a method to directly transform both aromatic and aliphatic aldehydes into either esters or amides has been developed. The success of this oxidative coupling depends on the appropriate choice of catalyst and organic oxidant, including the use of either alpha,alpha,alpha-trifluoroacetophenone or excess aldehyde. Mechanistic data that supports a catalytic cycle involving oxidative addition into the aldehyde C-H bond is also presented.

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Three-component coupling reaction of terminal alkyne, sulfonyl azide, and amine for the synthesis of N-sulfonyl amidine was developed using heterogeneous Cu@C catalyst, which was generated by pyrolysis of HKUST-1 (Cu3(BTC)2, BTC = 1,3,5-benzenetricarboxylate). A variety of terminal alkynes, sulfonyl azides, and amines underwent three-component coupling in the presence of 5 mol % Cu@C. The used Cu@C catalyst was readily separated by centrifugation and could be reused at least three times with no loss of reactivity. Filtration experiments revealed that the developed Cu@C catalysis is basically heterogeneous.

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An exoselective copper-catalyzed arylation- and vinylation-carbocyclization of electron-deficient alkenes was developed to provide rapid and efficient access to a variety of functionalized 3,3-disubstituted oxindoles. With this method, a highly efficient and concise formal synthesis of (±)- physostigmine and (±)-physovenine has been completed.

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An efficient transition-metal-free fluoroarylation reaction of N-aryl diazoacetamides with NFSI (N-fluorobenzenesulfonimide) is described. This reaction directly provides 3-fluorooxindole derivatives in yields of 67-93% with high selectivity via a carbene-free process under mild reaction conditions.

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A novel copper-catalyzed C(sp3)-N coupling of cycloketone oxime esters with nitrogen nucleophiles has been realized. All of the N-aryl/alkylanilines, anilines and benzophenone imine could be employed in this protocol to produce a variety of 1, 2 and 3 alkyl amines in one or two steps. These resultant cyano-containing alkyl amines were proven to be versatile synthetic building blocks in a variety of chemical transformations.

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Reactions of thiocarbonyl fluoride derived from cheap, readily available, and widely used CF3SiMe3, elemental sulfur, and KF with secondary amines and primary amines at room temperature in THF provided a wide variety of thiocarbamoyl fluorides and isothiocyanates in moderate to excellent yields, respectively. The two reactions show broad substrate scope and good functional group tolerance. Moreover, AgSCF3 reacts with secondary/primary amines under KBr at room temperature, affording quantitative thiocarbamoyl fluorides/isothiocyanates, which feature late-stage application.

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A facile and practical method that the copper powder-catalyzed Ullmann amination of aryl halides with aqueous methylamine under organic solvent-and ligand-free condition at 100 C and in air gave N-arylamines as sole products in good to excellent yields. The presence of a small amount of air is essential. Other aliphatic primary amines show good to very high reactivity. Secondary amines and aniline are not reactive. Sensitive substituents (i.e., CHO, MeCO, CN and Cl) are tolerable in the reaction.

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We have previously described a novel series of low molecular weight protein tyrosine kinase inhibitors which we named tyrphostins.The characteristic active pharmacophore of these compounds was the hydroxy-cis-benzylidenemalonitrile moiety.In this article we describe three novel groups of tyrphostins: (i) one group has the phenolic moiety of the cis-benzylidenemalononitrile replaced either with other substituted benzenes or with heteroaromatic rings, (ii) another is a series of conformationally constrained derivatives of hydroxy-cis-benzylidenemalononitriles in which the malononitrile moiety is fixed relative to the aromatic ring, and (iii) two groups of compounds in which the position trans to the benzenemalononitrile has been substituted by ketones and amides.Among the novel tyrphostins examined we found inhibitors which discriminate between the highly homologous EGF receptor kinase (HER1) and ErbB2/neu kinase (HER2).These findings may lead to selective tyrosine kinase blockers for the treatment of diseases in which ErbB2/neu is involved.

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Electrophilic substitutions of donor-substituted arylamines using tricarbonyliron-complexed cyclohexadienylium cations lead regio- and stereoselectively to the corresponding tricarbonylcyclohexadieneiron complexes.The C-C bond formation occurs regioselectively in the ortho position with respect to the amino group with arylamines containing a substituent in the para position.The initially formed N-alkylated arylamine (kinetic product) is shown to rearrange in an intermolecular process to the C-alkylated arylamine (thermodynamic product).The reported oxidative cyclization to the 3-methylcarbazole yields large amounts of the demetalated ligand.However, oxidative cyclization to the 3-methoxycarbazole is possible under mild reaction conditions (room temperature) by using especially activated manganese dioxides. Key words: Cylohexadienylium ligands / Substitutions, electrophilic / Cyclohexadiene ligands / Cyclizations, oxidative / Carbazoles / Iron complexes

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