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Novel bifunctional thiourea-ammonium salt catalysts derived from amino acids: Application to highly enantio- and diastereoselective aza-Henry reaction

The development of new efficient and easily accessible catalysts has been one of the focuses in asymmetric phase-transfer catalysis. In this paper, a novel class of chiral bifunctional thiourea-ammonium phase-transfer catalysts were synthesized from commercially available alpha-amino acids. The structural modularity of these catalysts permits facile tunings to achieve optimum results, which was demonstrated in catalyzing the aza-Henry reaction with excellent enantioselectivities (up to 99.5% ee) and diastereoselectivities (up to >25:1 dr).

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Catalytic, enantioselective N-acylation of lactams and thiolactams using amidine-based catalysts

In contrast to alcohols and amines, racemic lactams and thiolactams cannot be resolved directly via enzymatic acylation or classical resolution. Asymmetric N-acylation promoted by amidine-based catalysts, particularly Cl-PIQ 2 and BTM 3, provides a convenient method for the kinetic resolution of these valuable compounds and often achieves excellent levels of enantioselectivity in this process. Density functional theory calculations indicate that the reaction occurs via N-acylation of the lactim tautomer and that cation-pi interactions play a key role in the chiral recognition of lactam substrates.

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A process for preparing ealy grewe department his method (by machine translation)

The invention discloses a […] his preparation method. Ealy grewe department he a kind of effective specific glucose ceramide synthase inhibitor, can be used for treating I treat Gaucher spear. The invention provides a method for synthesizing […] he, the preparation method comprises: 1, 4 – benzodioxane – 6 – formaldehyde with a chiral ligand generating diastereoselective Aldol reaction, of after the reduction reaction, and then by the substitution and Staudinger reaction, then by the amidation reaction ealy grewe department he. The method raw materials are easy, simple operation, high yield and purity, and is easy for industrial production. (by machine translation)

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Asymmetric transfer hydrogenation of ketones using Ru(0) nanoparticles modified by Chiral Thiones

The catalytic asymmetric transfer hydrogenation (ATH) of acetophenone in isopropanol by Ru(0) nanoparticles (NPs) obtained by the in-situ reduction of Ru (II) half-sandwich complexes of chiral 2-oxazolidinethiones and 2-thiozolidinethiones was examined and compared with the catalytic activity of Ru(0) NPs formed in-situ by the reduction of [Ru(p-cymene)(Cl)2]2 in presence of optically active ligands such as (S)-4-isobutylthiazolidine-2-thione, (S)-4-Isopropyl-2(?2-pyridinyl)-2-oxazoline, (8S, 9R)-(?)-cinchonidine, (S)-leucinol, (S)-phenylalaninol, and (S)-leucine. Three of the best catalytic systems were then examined for ATH of thirteen aromatic ketones with different electronic and steric properties. A maximum of 24% ee was obtained using NPs generated from the Ru (II) half-sandwich complex with (S)-4-isobutylthiazolidine-2-thione in the TH of acetophenone. The NPs were characterized by TEM and DLS measurements. Kinetic studies and poisoning experiments confirmed that the reaction is catalyzed by the chiral NPs formed in-situ. Complete characterization of the complexes, including the X-ray crystallographic characterization of two complexes, was also carried out.

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Synthesis and Fungicidal Activity of Simple Structural 1,3-Thiazolidine-2-Thione Derivatives

A series of simple structural 1,3-thiazolidine-2-thione derivatives with various substituents on the S-, N-, 4-, and 5-positions was synthesized with high yields from various vicinal amino alcohols via two steps and screened for their antifungal activity. Bioassay results reveal that some thiazolidine-2-thione derivatives show strong antifungal activities against P. capsici, G. zeae, S. sclerotiorum, A. alternata, B. cinerea, or R. solani. The SAR analysis indicates that N-acyl substituted and 4-alkyl substituents can enhance the antifungal activity. Notably, 4-isopropyl-N-propionylthiazoldine-2-thione shows excellent activity against B. cinerea and G. zeae with IC50 values at 3.7 g/mL and 6.5 g/mL, respectively, and 4-isobutyl-N-propionylthiazoldine-2-thione shows remarkable fungicidal activity against R. solani, S. sclerotiorum, and G. zeae with IC50 values at 1.0 g/mL, 12.1 g/mL, and 11.0 g/mL, respectively. GRAPHICAL ABSTRACT.

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Discovery of potent, isoform-selective inhibitors of histone deacetylase containing chiral heterocyclic capping groups and a N-(2-aminophenyl)benzamide binding unit

The synthesis of a novel series of potent chiral inhibitors of histone deacetylase (HDAC) is described that contain a heterocyclic capping group and a N-(2-aminophenyl)benzamide unit that binds in the active site. In vitro assays for the inhibition of HDAC1, HDAC2, HDAC3-NCoR1, and HDAC8 by the N-(2-aminophenyl)benzamide 24a gave respective IC50 values of 930, 85, 12, and 4100 nM, exhibiting class I selectivity and potent inhibition of HDAC3-NCoR1. Both imidazolinone and thiazoline rings are shown to be effective replacements for the pyrimidine ring present in many other 2-(aminophenyl) benzamides previously reported, an example of each ring system at 1 muM causing an increase in histone H3K9 acetylation in the human cell lines Jurkat and HeLa and an increase in cell death consistent with induction of apoptosis. Inhibition of the growth of MCF-7, A549, DU145, and HCT116 cell lines by 24a was observed, with respective IC50 values of 5.4, 5.8, 6.4, and 2.2 mM.

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A versatile synthesis of various substituted taurines from vicinal amino alcohols and aziridines

Taurine and structurally diverse substituted taurines have been synthesized by peroxyformic acid, oxidation of the thiazolidine-2-thione intermediates generated from, vicinal amino alcohols or aziridines and carbon disulfide. The stereochemistry and mechanisms of the reactions are disscussed. The method is a salt-free and versatile route, convenient in terms of purification, and can be used to synthesize optically active substituted taurines.

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Thorpe-Ingold effect in the reaction of vicinal amino primary alcohol hydrogen sulfates and carbon disulfide

The Thorpe-Ingold effect is a key factor that affects the ring-closure rates and efficiency, as well as the structure of products in some ring-closure reactions. The reaction of vicinal amino primary alcohol hydrogen sulfates and carbon disulfide in the presence of potassium hydroxide produces the desired 4,4-disubstituted thiazolidine-2-thiones, and their isomers 5,5-disubstituted derivatives companying with their oxygen analogues 4,4-disubstituted oxazolidine-2-thiones. The formation of 5,5-disubstituted thiazolidine-2-thiones was rationalized via 2,2-disubstituted aziridine-1-carbodithioate intermediates, which were generated due to the Thorpe-Ingold effect. 4,4-Disubstituted oxazolidine-2-thiones were generated from carbon disulfide and free amino alcohols yielded via basic hydrolysis of active amino alcohol hydrogen sulfates in the reaction system.

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Kinetic resolution of N-acyl-thiolactams via catalytic enantioselective deacylation

Methanolysis of N-acyl-thiazolidin-2-thiones and -oxazolidin-2-thiones in the presence of acyl transfer catalyst benzotetramisole (BTM) proceeds in a highly enantioselective fashion thus enabling kinetic resolution of these substrates.

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Crystal and molecular structures of racemic and chiral 4-phenyl-1,3-thiazolidine-2-thiones

The crystal and molecular structures of (rac)- and (S)-4-phenyl-1,3-thiazolidine-2-thiones (4-PTT) have been studied by X-Ray diffraction and ab initio MO calculations at the level of HF/6-31G*. In racemic crystals, the thioamide groups of the enantiomeric (R)- and (S)-4-PTT pairs are hydrogen-bonded around a crystallographic center of symmetry to form a planar cyclic dimer. On the other hand, in (S)-4-PTT crystals, a cyclic dimer through the hydrogen bonding is formed between the two independent molecules (molecules A and B) in the asymmetric unit and its geometry is distorted.

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