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An organocatalytic enantioselective direct alpha-heteroarylation of aldehydes with isoquinoline: N -oxides

A new protocol for the enantioselective direct alpha-heteroarylation of aldehydes with isoquinoline N-oxides, via chiral enamine catalysis, has been successfully developed. High enantiomeric excesses and moderate to good yields were achieved for a variety of alpha-heteroarylated aldehydes.

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Novel MnII coordination compounds constructed from benzoate and various bipyridyl ligands: Magnetic property and catalytic activity

Three new MnII-benzoates coordination polymers containing various bipyridyl ligands (3,3?-dipicoylamine (3), 3-methylisoquinoline (4), and 4,4?-dithiopyridine (5)) and a [Mn6(O 2CPh)10(mu4-OH)2(CH 3OH)3(H2O)]¡¤1.5(C4H 4N2) cluster (1) have prepared and their structures were determined. The bipyridyl ligands can act as bridging ligands to produce 1-D or 2-D polymeric compounds. The pyrazine produced a Mn6 cluster molecule, and 3-methylisoquinoline did a benzoate-bridged 1-D MnII compound. The Mn6 cluster (1) and 1-D MnII compounds (3) and (4) show antiferromagnetic property. The compounds 1, 3, and 4 have catalyzed efficiently the transesterification of a variety of esters, while 5 has displayed a very slow conversion. The thermal stabilities of these complexes were also examined.

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35Cl Nuclear Quadrupole Resonance Studies of Hydrogen Bonding in Solid Complexes of Chlorobenzoic Acids with Amines

35Cl nuclear quadrupole resonance studies of hydrogen-bonded adducts containing o-, m- and p-chlorobenzoic acid and 2,6-dichlorobenzoic acid have been carried out.Average frequencies are correlated with DeltapKa values in terms of the proton-transfer model.The results obtained for various proton donors are compared and discussed taking into account both intra and intermolecular effects.

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Gold Particles Supported on Amino-Functionalized Silica Catalyze Transfer Hydrogenation of N-Heterocyclic Compounds

In this work we demonstrate that exceptionally small gold particles (d=0.6¡À0.2 nm) supported on amino-functionalized mesoporous silicate SBA-15 are highly active in transfer hydrogenation of structurally diverse unsaturated N-heterocyclic compounds. The heterocyclic ring is reduced selectively. The gold particles aggregate to a diameter of 4?5 nm in the presence of formic acid/triethylamine (hydrogen donor) during the first catalytic run. In subsequent cycles the nanoparticles maintain their size, yielding a very stable catalytic system that was recycled more than five times. In contrast, analogous SBA catalysts featuring larger (?5?35 nm) gold particles are not active. Excess formic acid also leads to the formation of formamide derivatives of the products of hydrogenation, which can be deformylated quantitatively. Fifteen structurally different substrates, including the scaffolds of quinoline, isoquinoline, quinoxaline, acridine, phenanthroline, quinazoline, and phenanthridine are hydrogenated and deformylated to give the amine products in >90% overall yield. Deuterium labeling experiments indicate that 1,2-addition with subsequent disproportionation of the formed intermediate is the preferred reaction path over the 1,4-addition one, suggesting the participation of a gold hydride species. (Figure presented.).

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MnO2/TiO2 catalyzed synthesis of coenzyme pyridoxamine-5?-phosphate analogues: 3-deoxypyridoxamine-5?-phosphate

The highly efficient-selective synthetic route of the pyridoxal-5?-phosphate (vitamin B6, PLP) analogues: C3 substituted deoxy derivatives of pyridoxal (PL), pyridoxal-N-oxide (PLNO), pyridoxamine (PM), pyridoxamine-5?-phosphate (PMP) and pyridoxal-5?-phosphate (PLP), were developed via reduction and followed by selective oxidation in one pot using solid supported nanoparticles. The salient features of this strategy are: economic two-fold conversion, more Lewis acid sites, vacancies on the nanoparticle surfaces, and good yields of 3-deoxypyridoxal and 3-deoxypyridoxamine-5?-phosphate.

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Three-component coupling reactions of isoquinolines, dimethyl acetylenedicarboxylate and indoles: a facile synthesis of 3-indolyl-1,2-dihydro-2-isoquinolinyl-2-butenedioate

A three-component coupling of isoquinolines, dimethyl acetylenedicarboxylate (DMAD) and indoles is achieved for the first time to produce dimethyl (E)-2-[1-(1H-3-indolyl)-1,2-dihydro-2-isoquinolinyl]-2-butenedioates in excellent yields and with high selectivity. The reaction proceeds smoothly at room temperature without a catalyst. Quinoline, DMAD and indole also undergo smooth coupling to furnish dimethyl (E)-2-[2-(1H-3-indolyl)-1,2-dihydro-1-quinolinyl]-2-butenedioate under similar conditions. This method is very useful to functionalize both indoles and aza-aromatic compounds in a one-pot operation.

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Spirooxazines and use thereof in the field of ophthalmic optics

The invention relates to photochromic compounds of general formula: STR1 in which: Ra and Rb denote hydrogen; alkyl; OR, SR, COR or COOR where R denotes hydrogen, alkyl, aryl or heteroaryl; a group NR1 R2 where R1 R2 denotes hydrogen, C4 -C7 alkyl or cycloalkyl, aryl, or form with the nitrogen a C4 -C7 heterocycle; NO2, CN, SCN or a halogen; a group SO3 R’ where R’ denotes hydrogen or an alkali metal; a mono- or polyhaloalkyl; m denotes an integer from 1 to 4 and n is equal to 1 or 2; Cy denotes an aromatic ring or an aromatic or non-aromatic heterocycle; Rc denotes an alkyl, allyl, phenyl or arylalkyl group which is mono- or disubstituted with alkyl, alkoxy or NO2 ; an alicyclic, an aliphatic hydrocarbon containing one or more hetero atoms; Rd, Re, Rf and Rg denote hydrogen, alkyl, alkoxy or thioalkyl or form in pairs a 4- to 7-membered cycloalkyl possibly containing hetero atoms which are optionally condensed with an aromatic ring; Rh denotes hydrogen or forms with Rd a 5- or 6-membered cycloalkyl; and the use thereof in ophthalmic optics.

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SUBSTITUTED PYRIDONES AS INHIBITORS OF POLY(ADP-RIBOSE) POLYMERASE (PARP)

The present invention discloses and claims a series of 2,3,5-substituted pyridone derivatives as defined herein. This invention also relates to methods of making these compounds. The compounds of this invention are inhibitors of poly(adenosine 5′-diphosphate ribose) polymerase (PARP) and are therefore useful as pharmaceutical agents, especially in the treatment and/or prevention of a variety of diseases, including diseases associated with the central nervous system and cardiovascular disorders.

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Synthesis of novel tetrahydrobenzazepine derivatives and their cytoprotective effect on human lymphocytes

Cytoprotective compounds such as amifostine play an important role in chemo- and radiotherapy due to their ability to reduce the side effects of these treatments. Our work was initiated with the intention to design, synthesise and test a new class of heterocyclic compounds that would have an antioxidative profile with the potential to be further developed as cytoprotective agents. The design was based on the privileged tetrahydrobenzazepine scaffold found in many natural products with a wide rangeof biological properties. This structure was further functionalised with moieties known to possess antioxidative features such as tertiary amine and styrene double bond. A series of eight tetrahydrobenzazepine derivatives of isoquinoline, 3,4-dihydro-beta-carboline and pyridine were synthesised employing the Heck reaction as a key transformation. Some of the prepared compounds were tested for their in vitro effects on chromosome aberrations in peripheral human lymphocytes using the cytochalasin-B blocked micronucleus (MN) assay. Three tetrahydrobenzoazepine derivatives showed significant cytoprotective properties, comparable or even better to those of the radioprotective agent amifostine.

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Benzylation of heterocyclic N-oxides via direct oxidative cross-dehydrogenative coupling with toluene derivatives

A novel cross-dehydrogenative coupling (CDC) of heterocyclic N-oxides with toluene derivatives has been discussed, allowing for the facile synthesis of a broad range of structurally diverse C1-benzyl quinoline N-oxides, isoquinoline N-oxides and pyridine N-oxides, including two methylated quinoline N-oxides in particular. This protocol not only extends the application of toluenes in synthetic organic chemistry, but also offers an alternative method to prepare benzylated heterocyclic N-oxides without any metal involved, which is important in medicinal chemistry.

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