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Unique alpha-hemiaminal ether gold carbene intermediates were accessed by a gold-catalysed 1,1-carboalkoxylation strategy and evolved through a highly selective 1,2-N-migration. This skeletal rearrangement gave functionalised indenes, and isotopic labelling confirmed the rare C-N bond cleavage of the ynamide moiety. The effect of substituents on the migration has been explored, and a model is proposed to rationalise the observed selectivity.

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In this study, The HPG@KCC-1 NP was prepared through the ringopening polymerization of glycidol on the surface of KCC-1 to form HPG@KCC-1 and then HPG@KCC-1 NPs were functionalized using chlorodiphenylphosphine and phosphine-functionalized nanoparticles (HPG@KCC-1/PPh2) as a recyclable phosphorus ligand was obtained. Also, gold (III) complex of HPG@KCC-1/PPh2 ligand (HPG@KCC-1/PPh2/Au) was prepared which used for the cyclization of propargylic amines with CO2 to provide 2-oxazolidinones. High catalytic activity and ease of recovery from the reaction mixture using filtration, and several reuse times without significant losses in performance are additional eco-friendly attributes of this catalytic system.

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The mechanism of Lewis acid catalysed hetero-Michael addition reactions of weakly basic nucleophiles to alpha,beta-unsaturated ketones was investigated. Protons, rather than metal ions, were identified as the active catalysts. Other mechanisms have been ruled out by analyses of side products and of stoichiometric enone-catalyst mixtures and by the use of radical inhibitors. No evidence for the involvement of pi-olefin-metal complexes or for carbonyl-metal-ion interactions was obtained. The reactions did not proceed in the presence of the non-coordinating base 2,6-di-tert-butylpyridine. An excellent correlation of catalytic activities with cation hydrolysis constants was obtained. Different reactivities of mono- and dicarbonyl substrates have been rationalised. A 1H NMR probe for the assessment of proton generation was established and Lewis acids have been classified according to their propensity to hydrolyse in organic solvents. Bronsted acid-catalysed conjugate addition reactions of nitrogen, oxygen, sulfur and carbon nucleophiles are developed and implications for asymmetric Lewis acid catalysis are discussed.

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The invention relates to novel compounds of formula I which are inhibitors of deubiquitylating enzymes (DUBs) and/or desumoylating enzymes. In particular, the invention relates to the inhibition of ubiquitin C-terminal hydrolase 7 or ubiquitin specific peptidase 7 (USP7). The invention further relates to methods for the preparation of these compounds and to their use in the treatment of cancer.

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A series of sulfonic acid-functionalized (SO3H-functionalized) ionic liquids was synthesized and used as metal-free, highly selective and efficient catalysts for the direct amination of alcohols. Notably, the activities of the series of SO3H-functionalized ionic liquids were compared and a 92% isolated yield was obtained using 3-tetradecyl-1-(butyl-4- sulfonyl)imidazolium trifluoromethanesulfonate ([BsTdIM][OTf]) as the catalyst. Importantly, the catalytic system has wide substrate scope including benzylic, allyl, propargylic, aliphatic alcohols with sulfonamide, amide, carbamate, aromatic amine and N-heterocyclic compounds. Interestingly, the system was also suitable for a multi-gram scale direct amination of alcohols. Additionally, the reusable nature of [BsTdIM][OTf] makes this protocol more attractive and avoids the disposal and neutralization of acidic catalysts. Moreover, preliminary experiments indicated that this reaction should proceed via an SN1 pathway. Copyright

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A facile synthesis of novel dispiroheterocycles has been developed through one-pot [3+2] cycloaddition between isatins, amino acids, and aurones. Thirty different dispiroheterocycles were synthesized eusing this method which features mild conditions, convenient operation, and high efficacy. Evaluation of the bioactivity of these dispiroheterocyclic products revealed antiviral activity against tobacco mosaic virus (TMV).

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We herein describe a high-throughput small molecule microarray (SMM) method that enables quick and cost-effective identification of potent inhibitors of metalloproteases in an activity-dependent manner, thereby offering a rapid means for inhibitor discovery and profiling. The Royal Society of Chemistry 2006.

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The present invention concerns an auxochrome substituent for an oxidative dye coupler. The auxochrome substituent enables ready developer reaction with the coupler to form azomethine and leuco dyes. Manipulation of the auxochrome substituent enables a bathochromic or hypsochromic shift of the light absorbance by the azomethine dye formed with the auxochrome substituted coupler.

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TMAF (Me4NF) is a useful catalyst for the conjugate addition of oxazolidinone and thiols to a range of Michael acceptors including esters, ketones, nitroolefins and cinnamaldehyde.

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This paper investigates the thermal degradation of eight linear amines loaded with CO2 and H+. The degradation rate of these amines tends to decrease with chain length. Hexamethylenediamine, the diamine with the longest chain, was found to be the most thermally resistant of the eight amines under CO2 loading. Putrescine was the only amine under acid loading that was not thermally stable, suggesting that the reaction mechanism is initiated by H+. Ethylenediamine, 2-(2-aminoethoxy)ethanamine, hexamethylenediamine, and Diglycolamine reach a thermodynamic equilibrium with their degradation products. Ethylenediamine was also found to be the most corrosive amine tested.

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