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Enantiomeric recognition of amino acid salts by macrocyclic crown ethers derived from enantiomerically pure 1,8,9,16-tetrahydroxytetraphenylenes

Asymmetric synthesis of (R,R)- and (S,S)-1,8,9,16- tetrahydroxytetraphenylenes was achieved from starting material (2R,3R)-butane-2,3-diol and (2S,3S)-butane-2,3-diol respectively by utilizing a center-to-axis strategy. A series of crown ether compounds 20, 24, and 25 and their corresponding enantiomers derived from chiral tetrahydroxytetraphenylene were synthesized in enantiomerically pure forms. Enantiomeric recognition properties of these hosts toward l- and d-amino acid methyl ester hydrochloride were studied by the UV spectroscopy titration. The tetramer hosts (S,S,S,S,S,S,S,S)-20 and (R,R,R,R,R,R,R,R)-20 exhibited the best enantioselectivities toward l- and d-alanine methyl ester hydrochloride salt with KL/KD = 4.1 and KD/KL = 3.9, respectively. The new chiral macrocyclic hosts would further enrich the host-guest chemistry.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

Archives for Chemistry Experiments of (2S,3S)-Butane-2,3-diol

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Effect of Methyl Substitution on Conformation and Molecular Arrangement of BEDT-TTF Derivatives in the Crystalline Environment

Two methylated bis(ethylenedithio)tetrathiafulvalene (ET) derivatives, Me2ET and Me4ET were stereoselectively synthesized to examine the effect of methylation on conformations of dihydrodithiin rings and molecular arrangements in the crystalline state.Since the donating ability of Me2ET and Me4ET are similar to that of ET, the methylated ET derivatives are considered to be appropriate to investigate the “lattice pressure” effect on ET radical salts by changing the volume of donor molecules.The upper limit of an activation energy for the ring inversion of the dimethylated dihydrodithiin in solution was estimated to be 32 kJ mol-1 by 13C NMR spectroscopy.The X-ray structure analyses revealed that orientations of methyl groups are fixed to axial in Me2ET and to equatorial in Me4ET, accompanied by the change of molecular stacking.The “volume of a methyl group” was evaluated by comparing the molecular volumes of Me2ET and Me4ET with that of ET, and the effective volume for the axial methyl group turns out to be 15percent larger than that of the equatorial.The solid state 13C NMR (CP/MAS) spectra of ET and its derivatives showed that the chemical shifts of resonance lines reflect the conformations of dihydrodithiin rings in crystals.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Transition-Metal-Catalyzed Asymmetric Organic Synthesis via Polymer-Attached Optically Active Phosphine Ligands. 6. Asymmetric Hydrogenation with Polymer Catalysts Containing Optically Active Pendent Alcohols

Three acrylate comonomers, (S,S), (R,R) and racemic 1-methyl-2-hydroxypropyl acrylate (7a-c), were prepared from the corresponding isomers of 2,3-butanediol.The acrylates were copolymerized with ethylene dimethacrylate and N-acryloyl-(2S,4S)-4-(diphenylphosphino)-2-<(diphenylphosphino)methyl>pyrrolidine (8) to give cross-linked resins containing phosphinopyrrolidines and optically active alcohols.Polymers containing the 4,5-bis<(diphenylphosphino)methyl>-1,3-dioxolane unit (DIOP) were prepared by copolymerizing acrylates 7a-c with ethylene dimethacrylate and 2-p-styryl-4,5-bis<(tosyloxy)methyl>-1,3-dioxolane (1) and treating the polymers with an excess of sodium diphenylphosphide.Exchange of Rh(I) onto these polymers provided catalysts that hydrogenated 2-acetamidoacrylic acid in tetrahydrofuran.The enantiomeric excesses obtained with the polymer-bound catalysts varied with the structure of the pendent alcohol, suggesting the participation of the polymer-bound alcohol at the catalyst site to provide an alcohol-like environment.A difference in enantiomeric excess (ee) was noted when catalysts containing either R or S alcohols were used.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Tetrahydrofuran antifungals

A compound represented by the formula I STR1 wherein X is independently both F or both Cl or one X is independently F and the other is independently Cl; R1 is a straight or branched chain (C3 to C8) alkyl group substituted by one or two phosphate ester groups (e.g., a phosphate ester convertible in vivo into a hydroxy group) thereof or a pharmaceutically acceptable salt thereof and pharmaceutical compositions thereof useful for treating and/or preventing fungal infections are disclosed.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Synthesis of New Optically Active Crown Ethers

Optically active crown ethers 1a-11, 2, 3a,b, 4a,b, 5a,b and the analogue 6 are synthesized.The efficiency of these compounds as phase-transfer catalysts for a series of enantioselective reactions will be tested.This will be described in a following publication. Key Words: Crown ethers, chiral, optically active / Phase transfer catalysts

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. name: (2S,3S)-Butane-2,3-diol, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 19132-06-0, name is (2S,3S)-Butane-2,3-diol. In an article£¬Which mentioned a new discovery about 19132-06-0

Purification and characterization of L-2,3-butanediol dehydrogenase of Brevibacterium saccharolyticum C-1012 expressed in Escherichia coli

The L-2,3-butanediol dehydrogenase produced in E. coli JM109/pLBD2-CTC was purified by 5 steps. The molecular mass of this enzyme was estimated at 110 kDa and the subunit was measured to be 30 KDa. The L-BDH had some differences from the BDHs from other sources in substrate specificity, pI value, pH stability, effects of divalent cations, and organic acids.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Chicoric acid analogues as HIV-1 integrase inhibitors

The present study was undertaken to examine structural features of L- chicoric acid (3) which are important for potency against purified HIV-1 integrase and for reported cytoprotective effects in cell-based systems. Through a progressive series of analogues, it was shown that enantiomeric D- chicoric acid (4) retains inhibitory potency against purified integrase equal to its L-counterpart and further that removal of either one or both carboxylic functionalities results in essentially no loss of inhibitory potency. Additionally, while two caffeoyl moleties are required, attachment of caffeoyl groups to the central linking structure can be achieved via amide or mixed amide/ester linkages. More remarkable is the finding that blockage of the catechol functionality through conversion to tetraacetate esters results in almost no loss of potency, contingent on the presence of at least one carboxyl group on the central linker. Taken as a whole, the work has resulted in the identification of new integrase inhibitors which may be regarded as bis-caffeoyl derivatives of glycidic acid and amino acids such as serine and beta-aminoalanine. The present study also examined the reported ability of chicoric acid to exert cytoprotective effects in HIV-infected cells. It was demonstrated in target and Cell-based assays that the chicotic acids do not significantly inhibit other targets associated with HIV-1 replication, including reverse transcription, protease function, NCp7 zinc finger function, or replication of virus from latently infected cells. In CEM cells, for both the parent chicoric acid and selected analogues, antiviral activity was observable under specific assay conditions and with high dependence on the multiplicity of viral infection. However, against HIV, 1- and HIV-2-infected MT-4 cells, the chicoric acids and their tetraacetylated esters exhibited antiviral activity (50% effective concentration (EC50) ranging from 1.7 to 20 muM and 50% inhibitory concentration (IC50) ranging from 40 to 60 muM).

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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(R)- and (S)-Tricyclo<6.4.0.04,9>dodecane

The title compounds 6 have been prepared from rac. 1,4-dihydroxytricyclo<6.4.0.04,9>dodecane-7,10-dione (1).In this way the diastereomeric thioacetals 3 made from (-)-(R,R)-2,3-butanedithiol (2) could be separated by chromatography as well as was transformed into the pure enantiomers of 6. (S)-configuration was predicted for (-)-1 from its positive CD at 300 nm.This could be proved by X-ray diffraction analysis with abnormal dispersion of the diastereoisomer of 3 with the smaller RF value, which yields (-)-1 on hydrolysis.The relatively high rotation = 30 of6is explained by steric twisting.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Inhibition of topoisomerase II by ICRF-193, the meso isomer of 2,3-bis(2,6-dioxopiperazin-4-yl)butane: Critical dependence on 2,3-butanediyl linker absolute configuration

The bis(2,6-dioxopiperazine)s are a structurally and mechanistically unique class of topoisomerase II inhibitors that do not bind DNA and that do not stabilize topoisomerase II-DNA strand passing intermediates (“cleavable complexes”). The most effective topoisomerase II inhibitor in the bis(2,6-dioxopiperazine) series is ICRF-193 (meso or S*, R* isomer), with a meso 2,3-butanediyl linker connecting the dioxopiperazine rings. The two enantiomeric diastereomers, (R,R) and (S,S), of ICRF-193 possessing the two optically active 2,3-butanediyl linkers have been prepared from their respective optically pure 2,4-diaminobutanes via 2,3-diaminobutane-N,N,N?,N?-tetraacetic acid, esterification, and imide formation. Both in vivo and in vitro assays for catalytic inhibition of topoisomerase II were employed to show that the (S,S)-and (R,R)-isomers are almost inactive as topoisomerase II inhibitors. The data indicate that the meso stereochemistry of the alkanediyl linker is crucial for activity and provides additional evidence that the cytotoxicity of the bis(2,6-dioxopiperazine)s is due to their ability to inhibit topoisomerase II. Copyright

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Metal Complexes Containing Enantiopure Bis(diamidophosphite) Ligands in Asymmetric Allylic Substitution and Hydroformylation Reactions

Enantiopure bis(diamidophosphite) ligands with a heterocyclic terminal fragment derived from (R)- and (S)-N,N?-dimethyl-1,1?-binaphthyldiamine and bridging fragments derived from (S,S)-2,3-butanediol (a), (4R,5R)-4,5-di(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane (b), and (R)- and (S)-1,1?-bi-2-naphthol (c) were used to prepare the palladium complexes with general formula [Pd(eta3-2-CH3-C3H4)(P-P)][X] (X = PF6, 1a-(S;Sal,Sal;S), 1b-(R;Ral,Ral;R), 1b-(S;Ral,Ral;S), 1c-(R;Ral;R), 1c-(R;Sal;R); X = BPh4, 2a-(R;Sal,Sal;R), 2c-(R;Ral;R)), which have been fully characterized. The solid-state structure for complexes 1a-(S;Sal,Sal;S) and 1b-(R;Ral,Ral;R) has been determined by X-ray diffraction. The catalytic performance of the palladium complexes has been evaluated in asymmetric allylic alkylation and amination reactions with the benchmark substrate. The influence of the nature and absolute configuration of both the terminal and bridging fragments of the bis(diamidophosphite) ligands on the asymmetric induction is discussed. The best results in terms of enantioselectivity were obtained with 1c-(R;Ral;R), affording enantiomeric excesses up to 85% in both alkylation and amination reactions. A large match-mismatch effect between the absolute configurations of stereocenters of ligand c has been observed in the allylic amination process. Preliminary results in the rhodium-catalyzed asymmetric hydroformylation of styrene by using bis(diamidophosphite) ligands a, b, and c disclosed in all cases low enantiomeric discrimination for the branched aldehyde. Both for the allylic alkylation and for the hydroformylation reaction, a related monodentate diamidophosphite d, derived from (R)-N,N?-dimethyl-1,1?-binaphthyldiamine and (S)-borneol, was also tested. Palladium complexes of this monodentate ligand showed fairly good enantioselectivity in allylic alkylation, but with very low rate, while the rhodium complex of d rendered better enantioselectivity (37% ee) than the bidentate ligands a-c in the hydroformylation of styrene. (Figure Presented).

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate