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The synthesis of multifunctional spirocycles was achieved from common cyclic carboxylic acids (cyclobutane carboxylate, cyclopentane carboxylate, l-proline, etc.). The whole sequence included only two chemical steps?synthesis of azetidinones, and reduction into azetidines. The obtained spirocyclic amino acids were incorporated into a structure of the known anesthetic drug Bupivacaine. The obtained analogues were more active and less toxic than the original drug. We believe that this discovery will lead to a wide use of spirocyclic building blocks in drug discovery in the near future.

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The ionic liquid 1-butyl-3methylimidazolium tetrafluoroborate [BMIm][BF4] has demonstrated high efficiency when applied as a solvent in the oxidative nitro-Mannich carboncarbon bond formation. The coppercatalyzed cross-dehydrogenative coupling (CDC) between N-phenyltetrahydroisoquinoline and nitromethane in [BMIm][BF4] occurred with high yield under the described reaction conditions. Both the ionic liquid and copper catalyst were recycled nine times with almost no lost of activity. The electrochemical behavior of the tertiary amine substrate and beta-nitroamine product was investigated employing [BMIm][BF4] as electrolyte solvent. The potentiostatic electrolysis in ionic liquid afforded the desired product with a high yield. This result and the cyclic voltammetric investigation provide a better understanding of the reaction mechanism, which involves radical and iminium cation intermediates.

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As an extension of the successful dicyanopyrazine photoredox catalysts, a series of X-shaped push-pull molecules with a systematically altered structure were designed and facilely synthesized; their structure-property relationship was elucidated in detail via experimental as well as theoretical calculations. Dicyanopyrazines are proven to be powerful photoredox catalysts with a push-pull arrangement that allows facile property tuning by interchanging a particular part of the D-pi-A system. Changing the mutual position of the cyano acceptors and the methoxy, methylthio and thienyl donors as well as modifying the linker allowed wide tuning of the fundamental properties of the catalysts. Contrary to the currently available organic photoredox catalysts, we provided a series of catalysts based on a pyrazine heterocyclic scaffold with easy synthesis and further modification, diverse photoredox characteristics and wide application potential across modern photoredox transformations. The photoredox catalytic activities of the target catalysts were examined in a benchmark cross-dehydrogenative coupling and novel and challenging annulation reactions.

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In order to achieve reproducibility during iridium-photoredox and nickel dual-catalyzed sp3-sp2 carbon-carbon bond-forming reactions, we investigated the role that molecular oxygen (O2), solvent and light-source (CF lamp or blue LED) play in a variety of Ir-photoredox mediated transformations. The presence of O2 was discovered to be important for catalyst activation when air-stable Ni(II) precatalysts were used in DMF under CF lamp irradiation; however, O2 was not required for catalysis when conducted with Ni(COD)2 in the same reaction system. O2 is believed to promote rapid reduction of the Ni(II) precatalyst by Ir(II) to Ni(0). In addition to O2, the effects that solvent and light-source have on the dual-catalyzed decarboxylative cross-coupling reactions will be discussed. These findings have enabled us to develop a more robust dual-catalyzed decarboxylative cross-coupling protocol.

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Described herein are compounds, methods of making such compounds, pharmaceutical compositions and medicaments containing such compounds, and methods of using such compounds to treat or prevent diseases or disorders associated with the enzyme glycolate oxidase (GO). Such diseases or disorders include, for example, disorders of glyoxylate metabolism, including primary hyperoxaluria, that are associated with production of excessive amounts of oxalate.

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A catalytic oxidation system, a CuCl2-O2 system, was efficient for dehydrogenation of 1,2,3,4-tetrahydroisoquinolines to 3,4-dihydroquinolines.Oxidation of 1,2,3,4-tetrahydroquinoline was also carried out.

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An unprecedented alpha-allylation of amines was achieved by combining palladium catalysis and visible-light photoredox catalysis. In this dual catalysis process, the catalytic generation of allyl radical from the corresponding pi-allylpalladium intermediate was achieved without additional metal reducing reagents (redox-neutral). Various allylation products of amines were obtained in high yields through radical cross-coupling under mild reaction conditions. Moreover, the transformation was applied to the formal synthesis of 8-oxoprotoberberine derivatives which show potential anticancer properties.

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Porous cross-linked polymers (PCPs) with phosphorescent [Ru(bpy) 3]2+ and [Ir(ppy)2(bpy)]+ building blocks were obtained via octacarbonyldicobalt (Co2(CO) 8)-catalyzed alkyne trimerization reactions. The resultant Ru- and Ir-PCPs exhibited high porosity with specific surface areas of 1348 and 1547 m2/g, respectively. They are thermally stable at up to 350 C in air and do not dissolve or decompose in all solvents tested, including concentrated hydrochloric acid. The photoactive PCPs were shown to be highly effective, recyclable, and reusable heterogeneous photocatalysts for aza-Henry reactions, alpha-arylation of bromomalonate, and oxyamination of an aldehyde, with catalytic activities comparable to those of the homogeneous [Ru(bpy) 3]2+ and [Ir(ppy)2(bpy)]+ photocatalysts. This work highlights the potential of developing photoactive PCPs as highly stable, molecularly tunable, and recyclable and reusable heterogeneous photocatalysts for a variety of important organic transformations.

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The present invention provides compounds of Formula (I). wherein A and Z are as defined in the specification, and compositions comprising any of such novel compounds. These compounds are myeloperoxidase (MPO) inhibitors and may be useful for for the treatment and/or prophylaxis of atherosclerosis, heart failure, chronic obstructive pulmonary disease (COPD), and related diseases.

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The various alpha-aminophosphonates have been prepared from tertiary aromatic and aliphatic amines with P(O)H compounds via a tert -butyl hydroperoxide mediated cross-dehydrogenative coupling reaction, eliminating the need for transition-metal catalysts. The oxidation of tertiary amine by tert -butyl hydroperoxide generates an iminium cation intermediate. A further addition of P(O)H compound to iminium cation gives the desired product.

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