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We report a practical one-pot synthesis of dialkylammonium salts of anionic dinuclear ruthenium complexes having chelating diphosphine ligands, BINAPs and DPB, with formula of [NEt2H2][{RuCl(diphosphine)}2(mu-Cl) 3] [2a: diphosphine = 2,2?-bis-(diphenylphosphino)-1,1?-binaphthyl; 6a: 2,2?-bis(di(p-tolyl)phosphino)-1,1?-binaphthyl; 8a: 1,2-bis(diphenylphosphino)benzene]. Treatment of cationic ruthenium complexes, [RuCl(eta6-p-cymene)(diphosphine)]Cl (4) with a slight excess of NEt2H2Cl (5a) afforded 2a, 6a, and 8a in quantitative yields. Similar reactions with various dialkylammonium salts 5b-f gave the corresponding salts, [NR2H2][{RuCl(diphosphine)}2(mu-Cl) 3]. A one-pot mixture of BINAP or its derivative, [RuCl2(eta6-arene)]2, and NR2H2Cl produced salts of the anionic dinuclear complexes which can be applied as catalysts for the asymmetric hydrogenation of ketonic substrates such as acetol and methyl acetoacetate with high activity and high enantioselectivity. The anionic face-sharing bioctahedral structure of these complexes was confirmed by the X-ray analysis of 8a, which has two hydrogen bonds between two NH of the diethylammonium cation and two terminal chloro-ligands.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A concise total synthesis of dendrodolides A?D (1?4) has been accomplished in 10 steps from commercially available (R)-propylene oxide and 3-buten-1-ol as starting materials. The key steps involved in the synthesis are Jacobsen hydrolytic kinetic resolution, epoxide ring opening with 2-allyl-1, 3-dithiane, Yamaguchi esterification and ring-closing metathesis (RCM). In addition, a series of ester derivatives were prepared utilizing Yamaguchi esterification at the C-3 position of the dendrodolide core and screened for their efficacy against cancer cell lines.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A novel series of chiral dopants synthesized from (S)-1,2-propanediol and mesogenic carboxylic acids were characterized by FT-IR, 1H NMR, elemental analysis and their helical twisting properties were investigated by doping the chiral dopants into a nematic liquid crystal host (SLC-1717). The results show that, the helical pitch of N*-LC mixture exhibited a terminal alkyl chain length dependence and the molecular twisting power beta also exhibited a temperature dependence (increasing beta with increasing temperature).

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Reduction of fermentation-derived lactic acid (LA) offers a renewables-based pathway to propylene glycol (PG), a large-scale commodity chemical, currently manufactured by the oxidation of petroleum-derived propene. Complementing our previously described catalytic hydrogenation of LA to PG, we now report electrocatalytic hydrogenation (ECH) of LA in an aqueous electrolyte using constant current electrolysis. A reticulated vitreous carbon (RVC) electrode serves to agglomerate, support, and supply current to a 5% Ru/C powder catalyst, the same catalyst used in the classical hydrogenations. The ECH conditions are mild (ambient pressure, 70 C vs 1500 psi H2, 150 C) relative to the chemical hydrogenation. More surprisingly, the major electrohydrogenation product is lactaldehyde (LAL), with small quantities of PG also formed. Variable current studies in the range of 10-100 mA show an increase in product yields and a shift in selectivity toward PG with increasing current. Experiments carried out with different acids as electrolytes reveal a distinct effect of the anion on the yields of the two products. In situ ATR-FTIR studies of the ECH of LA point to a chelating bidentate carboxylate adsorption mode for lactate on the Ru surface and offer insight into the effects of electrolyte anions on surface adsorption and reactivity.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The present invention provides a compound of formula (II): an inhibitor of indoleamine 2,3-dioxygenase (IDO), which may be used as medicaments for the treatment of proliferative disorders, such as cancer, viral infections and/or autoimmune diseases. Its prodrugs are disclosed.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A series of new ether lipid-3′-azido-3′-deoxythymidine (AZT) conjugates (11a-g) were synthesized and evaluated for anti-HIV activity. The effect of chirality on the antiviral activity was examined through the synthesis of AZT conjugates bearing alkoxypropanols in the lipid portion of the molecule (11a-d). In addition, the long alkyl chain of alkoxyethyl ether lipid-AZT analogs was replaced with aromatic groups (11e-g), and the effect of this structural modification on activity is reported. The results of the biological tests indicate that analogs with a methyl group alpha to the phosphate moiety (11c,d) exhibit a marked degree of stereoselectivity with regard to their anti-HIV activity. Also, replacement of the long alkyl chain with aromatic groups in the oxyalkyl ether phospholipid-AZT conjugates leads to substantially more potent compounds (11e-g) with an anti-HIV activity comparable to that of AZT.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Compositions comprising stereocomplexes of enantiomeric polymer chains having individual repeat units formed from the reaction of an epoxide and cyclic anhydride. The compositions can be made by mixing two types of enantiomeric polymer chains having opposite absolute stereochemistry. The compositions can be used in applications such as biomedical applications and drug delivery applications.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The invention is directed to a method for treating a cyclooxygenase-2 mediated disease or condition in a mammalian patient at risk of a thrombotic cardiovascular event, wherein the patient is on aspirin therapy to reduce the risk of the thrombotic cardiovascular event, comprising orally concomitantly or sequentially administering to the patient a cyclooxygenase-2 selective inhibitor in an amount effective to treat the cyclooxygenase-2 mediate disease or condition, and a nitric oxide donating compound in accordance with Formula (I) or a pharmaceutically acceptable salt thereof, wherein the nitric oxide donating compound is administered in an amount effective to reduce the gastrointestinal toxicity caused by the combination of the cyclooxygenase-2 selective inhibitor and aspirin. Pharmaceutical compositions are also encompassed.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Alkali metals dissolve in amines and ethers to give visible and infrared absorption bands.The visible band is believed to be due to absorption by the alkali metal anion and the infrared band to absorption of light by the solvated electrons.The visible and circular dichroism spectra of sodium-potassium alloy dissolved in several optically active ethers and amines were examined.In all cases, no circular dichroism could be detected corresponding to the alkali anion transition.An excellent synthetic route for the formation of a variety of chiral polyethers and cyclic polyethers is described.The method uses the readily available, chiral ethyl (S)-(+)-lactate.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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An enzyme capable of reducing acetoin in the presence of NADH was purified from Mycobacterium sp. B-009, a non-clinical bacterial strain of soil origin. The enzyme is a homotetramer and can be classified as a medium-chain alcohol dehydrogenase/ reductase based on the molecular weight of the monomer. Identification of the structural gene revealed a limited distribution of homologous genes only among actinomycetes. In addition to its activity as a reductase specific for (S)-acetoin (EC 1.1.1.76), the enzyme showed both diacetyl reductase (EC 1.1.1.304) and NAD+ -dependent alcohol dehydrogenase (EC 1.1.1.1) activities. (S)-Acetoin and diacetyl reductases belong to a group of short-chain alcohol dehydrogenase/reductases but do not have superior abilities to dehydrogenate monoalcohols. Thus, the purified enzyme can be readily distinguished from other enzymes. We used the dual functionality of the enzyme to effectively reduce diacetyl to (S)-acetoin, coupled with the oxidation of 1-butanol.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate