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An efficient and mild protocol for regioselective synthesis of N-Nitroso aryl ketones by palladium-catalyzed direct acylation of arenes using N-Nitroso as directing groups is described. This reaction proceeded smoothly and could tolerate a variety of functional groups. Moreover, this chemistry offers a convenient access to a range of indazoles.

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Palladium catalysed C-N bond formation in supercritical carbon dioxide has been accomplished. Carbamic acid formation is avoided in part through the use of an N-silylamine as the coupling partner. Employing a catalyst system of Pd 2dba3 (1 mol%) and 2-dicyclohexylphosphino-2?, 4?,6?-triisopropyl-1,1?-biphenyl (X-Phos) (2 mol%) enabled the catalytic amination of aryl bromides and chlorides with N-silylanilines to be realised in excellent yield. Extension of the methodology to the N-arylation of N-silyldiarylamines, N-silylazoles and N-silylsulfonamides is reported. The Royal Society of Chemistry 2005.

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Transition-metal-free multicomponent reactions involving aryne precursors, secondary amines, and sulfuryl fluoride are reported herein. Zwitterionic intermediates formed from the reaction of arynes with amine nucleophiles can capture SO2F2 under mild conditions, offering a novel and practical protocol for the synthesis of 2-dialkyl-, 2-alkylaryl-, or 2-diarylamino-substituted arenesulfonyl fluoride derivatives in good to excellent yields.

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The reaction of 4-substituted N,N-dimethylanilines with N-substituted maleimides proceeds in the presence of a catalytic amount of manganese(II) nitrate under oxygen to give the corresponding N-substituted 1,2,3,4-tetrahydro-1-methylquinoline-3,4-dicarboximides along with N-methylanilines.

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(Chemical Equation Presented) A highly efficient palladium-catalyzed synthesis of unsymmetrically substituted 3-(diarylmethylenyl)indolinones from readily accessible starting materials is developed. The domino reaction involves a sequence of intermolecular carbopalladation, C-H activation, and C-C bond formation. A plausible mechanistic pathway for the reaction is discussed on the basis of the kinetic isotope effect [KH/KD (intermolecular) = 1, KH/KD (intramolecular) = 2.7] as well as the electronic effect.

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The P-phenylpropa-1,2-dienyl phosphinic amides 4a-h, the corresponding phosphinates 4i-k and the (1-phenylpropa-1,2-dienyl) phosphonic diamide 4l, whose amide N-atoms resp. ester O-atoms wear unsubstituted or substituted benzene nuclei, were formed by [2,3] sigmatropic rearrangement of the corresponding (2-alkynyloxy)phosphine derivatives 3a-l. Heating the solutions of 4a-l led in some cases to decomposition (see 4a-c), but in other cases to the tricycles 5d-l, which were formed by Intramolecular Diels-Alder (IMDA) reaction between the second allenic double bond as dienophile and the benzenic pi-system as diene.

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A cationic (CAAC)gold(I) complex promotes the addition of all types of nontertiary amines to a variety of alienes, affording allylic amines in good to excellent yields; the amino fragment always adds to the less substituted terminus of the CCC skeleton.

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The present invention relates to compounds of formula (I) wherein A, R1, R2, R3, R4, and R5 are as described herein, pharmaceutical compositions containing them, and methods for their manufacture. These compounds are 5-HT5A receptor antagonistsand are useful in the prevention and/or treatment of depression, anxiety disorders, schizophrenia, panic disorders, agoraphobia, social phobia, obsessive compulsive disorders, post-traumatic stress disorders, pain, memory disorders, dementia, disorders of eating behaviors, sexual dysfunction, sleep disorders, abuse of drugs, motor disorders such as Parkinson’s disease, psychiatric disorders or gastrointestinal disorders

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A copper-catalyzed activation of C(sp3)-H bonds of DMF at room temperature was developed, which results in methyl transfer to aromatic amines for efficient synthesis of exceedingly valuable alpha-amino nitriles. This process features excellent functional group tolerance, a broad substrate scope, and high activity under ambient conditions.

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A unique preference of tin(II) for aniline activation is disclosed. In the present work tin(II) triflate-catalyzed highly selective Markovnikov reductive hydroamination of internal as well as terminal alkynes is reported. The mechanistic study revealed the involvement of two steps in one pot wherein alkyne reduces to corresponding alkene in presence of PMHS as reducing agent followed by hydroamination of alkene. A broad range of alkynes transformed into tertiary amines with good to excellent yield. This method is equally applicable in synthesis of secondary amines.

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