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Chiral Compounds (chiral + compound)
Selected AbstractsEditorial: Biocatalysis in the Synthesis of Chiral CompoundsBIOTECHNOLOGY JOURNAL, Issue 5 2006Stefan Buchholz [source] Electrokinetic partial filling technique as a powerful tool for enantiomeric separation of DL -lactic acid by CE with contactless conductivity detectionELECTROPHORESIS, Issue 11 2007zslav Maier Dr. Abstract A modified partial filling method for chiral separation of DL -lactic acid as the model chiral compound with vancomycin chloride as the chiral selector was developed by CE with contactless conductivity detection. Electrokinetic partial filling technique (EK-PFT) was used as an alternative method to the conventional hydrodynamic partial filling method. EK-PFT, in contrast to the hydrodynamic partial filling technique, allowed the removal of the chloride counterions from the chiral selector which otherwise led to poor sensitivity in conductivity detection. The baseline separation of DL -lactic acid as the model analyte was achieved in 5,min in a polyacrylamide-coated capillary. The best resolution was achieved by electrokinetic partial filling of vancomycin cations from the injection solution containing 5,mmol/L oxalate L -histidinium at pH,4.5 with 10,mmol/L vancomycin chloride. Computer simulation was used to explain the observed phenomena in the boundary between the inject vial and the capillary during the EK-PFT of vancomycin cations. [source] Helical polyacetylene,Origins and synthesisTHE CHEMICAL RECORD, Issue 6 2008Kazuo Akagi Abstract We present the origins and synthesis of helical polyacetylene (H-PA) by focusing on its peculiar spiral morphology. Interfacial polymerization of acetylene was carried out in an asymmetric reaction field consisting of chiral nematic liquid crystal (N*-LC) and Ziegler,Natta catalyst. As the N*-LC is composed of nematic liquid crystal and a chiral compound such as a binaphthyl derivative with either the R - or S -configuration, the screw directions of the polyacetylene chain and fibril bundle,and even the spiral morphology,are rigorously controlled by the chirality of the selected compound. Interestingly, the screw directions of the fibril and the bundle in H-PA were found to be opposite to that of N*-LC. It is worthwhile to emphasize that the hierarchical spiral morphology involving the primary to higher order structure is generated in a synthetic polymer such as polyacetylene by using N*-LC as an asymmetric polymerization solvent. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 395,406; 2008: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20163 [source] Cover Picture: Biotechnology Journal 5/2006BIOTECHNOLOGY JOURNAL, Issue 5 2006Article first published online: 11 MAY 200 Cover illustration: Chirality is omnipresent in nature: Many compounds contain an asymmetric center and thus can occur in two non-superimposable mirror-image forms (enantiomers). The two enantiomers of a chiral compound often have dramatically different effects, as exemplified by the thalidomid catastrophe. Therefore, only one enantiomer is needed for the production of active substances in the pharmaceutical or agricultural industry. It is an important aspect in white biotechnology, to take advantage of highly specific catalysts of (micro-) biological origin for the synthesis of enantiopure compounds. Biocatalysis indeed is a highly efficient process and an example of environmentally friendly, ,green' chemistry, requiring relatively low energy inputs, mild solvents and generating minimal byproducts. Image © Wacker. [source] The Heteropolytungstate Core {BW13O46}11, Derived as Monomer, Dimer, and TrimerCHEMISTRY - A EUROPEAN JOURNAL, Issue 25 2007Nathalie Leclerc-Laronze Dr. Abstract A study of the borotungstate system has led to the characterization of new, original compounds based on the unconventional Keggin derivative [H3BW13O46]8, ion (denoted as 1). [H3BW14O48]6, (2) and the dimer [H6B2W26O90]12, (3) crystallize as mixed cesium/ammonium salts and have been characterized by single-crystal X-ray diffraction analysis. Anion 2 reveals an unusual arrangement, consisting of an outer {W3O9} core grafted onto the monovacant [BW11O39]9, Keggin moiety and exhibits an unprecedented distorted square-pyramidal arrangement for a cis -{WO2} core. Elemental analysis, supported by bond distance analysis, is consistent with the presence of three protons distributed over the terminal oxygens of the outer {W3O7} capping fragment. The [H6B2W26O90]12, ion (3) is formally derived from the direct condensation of two [H3BW13O46]8, subunits. The cisoid arrangement of the two [BW11O39]9, subunits, coupled with the antiparallel arrangement of the two quasi-linear OW,,,OWOH2 chains within the central {W4O12} connecting group, breaks any symmetry, thereby resulting in a chiral compound. Polarography and pH-metric titrations reveal the formation of the monomeric precursor [H3BW13O46]8, (anion 1) under stoichiometric conditions. 183W NMR analysis of 2 and 3 in solution gives complex spectra, consistent with the presence of equilibria between several species. In the frame of this study, we also report on a structural re-investigation of the [H6B3W39O132]15, ion (4) based on reliable results obtained in the solid state by means of single-crystal X-ray diffraction analysis, and in solution by means of 1D and 2D COSY 183W NMR. X-ray diffraction analysis revealed the presence of three attached aquo ligands on the central {W6O15} connecting core, generating three OW,,,OWOH2 quasi-linear chains, which are responsible for the chirality of the trimeric assembly. This structural arrangement accounts for the 39-line 183W solution spectrum. The 2D COSY spectrum permits reliable assignments of the six strongly shielded resonances (around ,250 and ,400,ppm) to the six central W atoms, as well as additional assignments. The origin of such strong shielding for these particular W atoms is discussed on the basis of previously published results. Infrared data for compounds 1, 3, and 4 are also presented. [source] Synthesis and Antiviral Activities of Chiral Thiourea DerivativesCHINESE JOURNAL OF CHEMISTRY, Issue 3 2009Zhikun YAN Abstract An environmentally benign method has been developed for the synthesis of novel chiral thiourea derivatives in high yields in ionic liquid [Bmim]PF6. The ionic solvent can be recovered and reused without any loss of its activity. The target compounds were characterized by elemental analysis, IR, 1H NMR and 13C NMR spectral data. According to the preliminary bioassay, some of the chiral thiourea analogues exhibited moderate in vivo antiviral activities against TMV at a concentration of 500 mg/L. Title chiral compound 3i was found to possess good in vivo protection, inactivation and curative activities of 57.0%, 96.4% and 55.0%, respectively against TMV with an inhibitory concentration at 500 mg/L. The title chiral compound 3i revealed better inactivation effect on TMV (EC50=50.8 µg/mL) than Ningnanmycin (EC50=60.2 µg/mL). [source] Induced circular dichroism in solid-state inclusion compoundsCHIRALITY, Issue 7 2001Koichi Tanaka Abstract In order to measure the circular dichroism (CD) spectrum in the solid state of a chiral compound which has no chromophore, an induced CD spectral method was developed by measuring the spectrum of the inclusion crystal of the chiral compound with a simple achiral aromatic host compound in the Nujol mulls. Chirality 13:347,350, 2001. © 2001 Wiley-Liss, Inc. [source] Achiral and chiral separations using MEKC, polyelectrolyte multilayer coatings, and mixed mode separation techniques with molecular micellesELECTROPHORESIS, Issue 6 2010Candace A. Luces Abstract Mixed mode (MM) separation using a combination of MEKC and polyelectrolyte multilayer (PEM) coatings is herein reported for the separation of achiral and chiral analytes. Many analytes are difficult to separate by MEKC and PEM coatings alone. Therefore, the implementation of a MM separation provides several advantages for overcoming the limitations of these well-established methods. In this study, it was observed that achiral separations using MEKC and PEM coatings individually resulted in partial resolution of eight very similar aryl ketones when the molecular micelle (sodium poly(N -undecanoyl- L -glycinate)) concentration was varied from 0.25 to 1.00%,w/v and the bilayer number varied from 2 to 4. However, when MM separation was introduced, baseline resolution was achieved for all eight analytes. In the case of chiral separations, temazepam, aminoglutethimide, benzoin, benzoin methyl ether, and coumachlor were separated using the three separation techniques. For chiral separations, the chiral molecular micelle, sodium poly(N -undecanoyl- L -leucylvalinate), was employed at concentrations of 0.25,1.50%,w/v for both MEKC and PEM coatings. Overall, the results revealed partial separation with MEKC and PEM coatings individually. However, MM separation enabled baseline separation of each chiral mixture. The separation of achiral and chiral compounds from different compound classes demonstrates the versatility of this MM approach. [source] Glycogen: A novel branched polysaccharide chiral selector in CEELECTROPHORESIS, Issue 6 2010Jiaquan Chen Abstract Various chiral selectors have been employed in CE and among them linear polysaccharides exhibited powerful enantioselective properties. Different from linear polysaccharides, the use of branched polysaccharides as chiral selectors in CE has not been reported previously. In this study glycogen belonging to the class of branched polysaccharides was used as a novel chiral selector for the enantiomeric separations for the first time. Since glycogen is electrically neutral, the method is applicable to ionic compounds. Eighteen chiral compounds including 12 basic drugs and six acidic drugs have been tested to demonstrate the potential of this chiral selector. BGE and selector concentrations and buffer pH were systematically optimized in order to obtain successful chiral separations. Among the tested compounds, the enantiomers of ibuprofen, which is an acidic drug, were successfully recognized by 3.0%,w/v glycogen with 90,mM Tris-H3PO4 buffer (pH 7.0). The enantiomers of basic drugs such as citalopram, cetirizine and nefopam were also baseline-resolved with 50,mM Tris-H3PO4 buffer (pH 3.0) containing 3.0% glycogen. Amlodipine belonging to basic compound only gave partial enantioseparation under the above-mentioned condition. [source] Chiral separation of the plant lignan matairesinol by capillary electrophoresis,ELECTROPHORESIS, Issue 17 2008Ulrike Müller Abstract Lignans are dimeric phenylpropanoid compounds in plants that enjoy increasing medicinal interest because of their phytoestrogen activity. Lignans are chiral compounds and for most natural occurring lignans, chirality is not known. Separation of racemic matairesinol by CE in a non-coated silica capillary with carboxymethyl-,-cyclodextrin as chiral selector in phosphate buffer was successful. Electrolyte and selector concentrations and pH were systematically optimized in order to obtain baseline separation and short analysis times. Matairesinol from safflower fruit was determined as (,)-enantiomer. Quantitation results for matairesinol with the optimized method after calibration with authentic lignan were very similar to those by HPLC. The limit of detection is 2,,g/mL sample by DAD detection. [source] Application of polymeric surfactants in micellar electrokinetic chromatography-electrospray ionization mass spectrometry of benzodiazepines and benzoxazocine chiral drugsELECTROPHORESIS, Issue 5-6 2006Jingguo Hou Abstract Chiral micellar EKC (CMEKC) coupled to ESI-MS using polymeric surfactants as pseudostationary phases is investigated for simultaneous enantioseparation of two benzodiazepines, (±)-oxazepam ((±)-OXA) and (±)-lorazepam ((±)-LOR), and one benzoxazocine, (±)-nefopam ((±)-NEF). First, enantioselectivity and electrospray sensitivity of six chiral polymeric surfactants for all three chiral compounds are compared. Second, using poly(sodium N -undecenoyl- L -leucinate) as pseudostationary phase, the organic modifiers (methanol (MeOH), isopropanol, and ACN) are added into the running buffer to further improve chiral resolution (RS). Next, a CMEKC-ESI-MS method for the simultaneous enantioseparation of two benzodiazepines is further developed by using a dipeptide polymeric surfactant, poly(sodium N -undecenoxy carbonyl- L,L -leucyl-valinate) (poly- L,L -SUCLV). The CMEKC conditions including nebulizer pressure, capillary length, ammonium acetate concentration, pH, poly- L,L -SUCLV concentration, and capillary temperature were optimized to achieve maximum chiral RS and highest sensitivity of MS detection. The spray chamber parameters (drying gas temperature and drying gas flow rate) as well as sheath liquid conditions (MeOH content, pH, flow rate, and ionic strength) were found to significantly influence MS S/N of both (±)-OXA and (±)-LOR. Finally, a comparative study between simultaneous UV and MS detection showed high plate numbers, better chiral RS, and enhanced detectability with CMEKC-MS. However, speed of analysis was faster using CMEKC-UV. [source] Emission of legacy chlorinated pesticides from agricultural and orchard soils in British Columbia, CanadaENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 6 2006Terry F. Bidleman Abstract Air samples were collected above agricultural fields in the Fraser Valley and orchards in the Okanagan Valley, British Columbia, Canada, to investigate volatilization of organochlorine pesticides used in the past. Concentrations of pesticides in air were elevated over soils that contained higher residues. Soil/air fugacity ratios at sites with the higher soil residues were calculated relative to air sampled at 40 cm height and background air. The fugacity ratios in the first case indicated net volatilization or soil-air equilibrium for most compounds and occasional net deposition for p,p, -dichlorodiphenyldichloroethene (p,p, -DDE), whereas those in the second case showed a strong potential for net volatilization of all compounds. The enantiomer fraction (EF) of chiral compounds ,-hexachlorocyclohexane (,-HCH), trans -chlordane, cis -chlordane, and o,p, -DDT were determined in overlying air samples and soils. Enantiomer fractions in air corresponded to those in soils at fields in which soil concentrations were high but were decoupled from soil signatures at fields with low soil residues. Mean EFs in air sampled over soils were significantly (p < 0.001) nonracemic for ,-HCH and the chlordanes and agreed with published EFs in regional ambient air. The mean EF of o,p, -DDT for all air samples did not show a significant deviation from racemic EFs (p > 0.2), but EFs of individual samples reflected the ambivalent nature of o,p, -DDT degradation, sometimes preferring the (+) enantiomer and other times the (,) enantiomer. The study indicates that soils are continuing to emit "legacy" pesticides into the regional atmosphere. [source] Synthesis and Evaluation of a Broad Range of New Chiral (Aminoalkyl)phosphane Ligands for Asymmetric Hydrogen-Transfer Reduction of Prochiral KetonesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 19 2003Matthieu Léautey Abstract Twenty new chiral (aminoalkyl)phosphane ligands have been prepared from four enantiomerically pure advanced chiral compounds. We describe their use for asymmetric hydrogen-transfer reduction of three prochiral ketones. Enantioselectivities up to 90% were obtained. We investigated the influence on the enantioselectivity of each part of these new (aminoalkyl)phosphane ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Perspectives on ecological risk assessment of chiral compoundsINTEGRATED ENVIRONMENTAL ASSESSMENT AND MANAGEMENT, Issue 3 2009Jacob K Stanley Abstract Enantiomers of chiral contaminants can significantly differ in environmental fate as well as in effects. Despite this fact, such differences are often ignored in regulation and in practice, injecting uncertainty into the estimation of risk of chiral compounds. We review the unique challenges posed by stereochemistry to the ecological risk assessment of chiral contaminants and existing regulatory guidance for chiral pharmaceuticals and pesticides in the United States. We identify the advantages of obtaining data on fate and effects of each individual enantiomer of chiral contaminants that are either distributed as or may end up as enantiomer mixtures in the environment due to enantiomerization. Because enantiomers of the same compound are highly likely to coexist in the environment with each other and can result in nonadditive effects, we recommend treatment of enantiomers as components of a mixture using widely accepted mixture models from achiral risk assessment. We further propose the enantiomer hazard ratio for retrospectively characterizing relative enantiomer risk and examine uncertainty factor magnitudes for effects analysis. [source] Asymmetric Hydrogenations (Nobel Lecture 2001)ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2003William Abstract The start of the development of catalysts for asymmetric hydrogenation was the concept of replacing the triphenylphosphane ligand of the Wilkinson catalyst with a chiral ligand. With the new catalysts, it should be possible to hydrogenate prochiral olefins. Knowles and his co-workers were convinced that the phosphorus atom played a central role in this selectivity, as only chiral phosphorus ligands such as (R,R)-DIPAMP, whose stereogenic center lies directly on the phosphorus atom, lead to high enantiomeric excesses when used as catalysts in asymmetric hydrogenation reactions. This hypothesis was disproven by the development of ligands with chiral carbon backbones. Although the exact mechanism of action of the phosphane ligands is not incontrovertibly determined to this day, they provide a simple entry to a large number of chiral compounds. [source] Non-Linear Effect of Modifier Composition on Enantioselectivity in Asymmetric Hydrogenation over Platinum MetalsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2003Wolf-Rüdiger Huck Abstract Prominent non-linear behavior was observed when mixtures of cinchona alkaloids were applied as chiral modifiers in enantioselective hydrogenations over Pt/Al2O3 and Pd/TiO2. The phenomenon is traced to differences in the strength and geometry of alkaloid adsorption on the metal surface. In ethyl pyruvate hydrogenation under close to ambient conditions the weaker adsorbing quinidine (QD) outperformed the generally preferred modifier cinchonidine (CD) and afforded the highest ee (96,98%) at 1,5,bar. In the partial hydrogenation of 4-methoxy-6-methyl-2-pyrone to the dihydro derivative 4 CD gave 73% ee to (S)- 4 and QD provided 72% ee to (R)- 4, and still the alkaloid mixture containing less than 5,mol,% CD afforded 15% ee to (S)- 4. This non-linear behavior may be advantageous in asymmetric synthesis as low purity chiral compounds can be applied as efficient modifiers for Pt or Pd. [source] Chiral polymers for resolution of enantiomersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2009Yoshio Okamoto Abstract In 1979, the formation of one-handed helical poly(triphenylmethyl methacrylate) (PTrMA) was found through the helix-sense-selective polymerization of methacrylate using chiral anionic initiators, and the existence of a stable helical polymer without chiral side chains was proved. The chiral polymer exhibited unexpected high chiral recognition of various racemic compounds when used as the chiral packing material (CPM) for HPLC, which was commercialized in 1982 as the first chiral column based on an optically active polymer. This success encouraged us to develop further useful commercial chiral packing materials (CPMs) based on polysaccharides, cellulose, and amylose. By using these polysaccharide-based CPMs, particularly phenylcarbamate derivatives, nearly 90% of chiral compounds can be resolved not only analytically but also preparatively, and several chiral drugs have been produced using the CPMs. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1731,1739, 2009 [source] Synthesis and characterization of novel liquid-crystalline copolymers containing thermally stable photochromic groupsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2007Jui-Hsiang Liu Abstract To overcome the defects of the thermal instability of azobenzene, a series of novel photochromic, chiral, liquid-crystalline monomers and polymers were synthesized from (+)-camphor. The copolymerization of the photochromic monomers with comonomers was carried out. The synthesized monomers and polymers were identified with nuclear magnetic resonance, Fourier transform infrared, and elemental analysis. The composition of the copolymers was estimated with elemental analysis. The specific rotation of the chiral compounds and polymers was evaluated. The thermal stability and phases of the polymers during heating and cooling cycles were studied with differential scanning calorimetry and thermogravimetric analysis. The phases of the polymers were identified with polarized optical microscopy textures and X-ray diffraction analysis. The distance between the layers of smectic liquid crystals was estimated from the diffraction angles. Photoisomerization of the configurational E/Z structures was investigated with an ultraviolet,visible spectrophotometer with 300-nm ultraviolet irradiation. The thermal stability of the Z-structural segment in the polymers was confirmed through the heating of the polymer at 70 °C for over 10 h. The photoisomerization and thermal stability of the CC bond in the polymeric materials were demonstrated through a series of novel chiral polymers synthesized in this investigation. Both the polarity of the center part and the molecular length at the ends of the molecules were found to be necessary factors for the formation of liquid-crystalline molecules. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2026,2037, 2007 [source] Absolute enantioselective separation: Optical activity ex machinaJOURNAL OF SEPARATION SCIENCE, JSS, Issue 17 2005Roman Bielski Abstract The paper describes methodology of using three independent macroscopic factors affecting molecular orientation to accomplish separation of a racemic mixture without the presence of any other chiral compounds, i. e., absolute enantioselective separation (AES) which is an extension of a concept of applying these factors to absolute asymmetric synthesis. The three factors may be applied simultaneously or, if their effects can be retained, consecutively. The resulting three mutually orthogonal or near orthogonal directors constitute a true chiral influence and their scalar triple product is the measure of the chirality of the system. AES can be executed in a chromatography-like microfluidic process in the presence of an electric field. It may be carried out on a chemically modified flat surface, a monolithic polymer column made of a mesoporous material, each having imparted directional properties. Separation parameters were estimated for these media and possible implications for the natural homochirality are discussed. [source] Autocatalytic Enantiomerisation at the Crystal Surface in Deracemisation of Scalemic ConglomeratesCHEMISTRY - A EUROPEAN JOURNAL, Issue 39 2009Shengwei Wei Dr. Abstract Deracemisation of racemic or scalemic conglomerates of intrinsically chiral compounds appears to be a promising method of chiral resolution. By combining the established methods of asymmetric synthesis and the physical process of crystal growth, we were able to achieve a complete deracemisation (with 100,%,ee) of an asymmetric Mannich product conglomerate,vigorously stirred in its saturated solution,from a starting enantiomeric excess value of 15.8,% in the presence of pyrrolidine (8,mol,%) as an achiral catalyst for the CC bond-forming reaction. Strong activation of this deracemisation process was observed on mild isothermal heating to only 40,°C, resulting in dramatic acceleration by a factor of about 20 with respect to the results obtained at room temperature. Despite the fact that the racemisation half-life time of the nearly enantiopure Mannich product (with 99,%,ee) in the homogenous solution at the reaction temperature is eight days, the deracemisation process took only hours in a small-scale experiment. This apparent paradox is explained by a proposed rapid enantiomerisation at the crystal/solution interface, which was corroborated by a 13C labelling experiment that confirmed the involvement of rapid enantiomerisation. Frequent monitoring of the solution-phase ee of the slowly racemising compound further revealed that the minor enantiomer dominated in solution, supporting an explanation based on a kinetic model. A generalisation of the process of "aymmetric autocatalysis" (resulting in automultiplication of chiral products in homogenous media) to encompass heterogeneous systems is also suggested. [source] Bifunctional Catalysis by Natural Cinchona Alkaloids: A Mechanism ExplainedCHEMISTRY - A EUROPEAN JOURNAL, Issue 32 2009Clotilde Abstract The use of bifunctional chiral catalysts, which are able to simultaneously bind and activate two reacting partners, currently represents an efficient and reliable strategy for the stereoselective preparation of valuable chiral compounds. Cinchona alkaloids such as quinine and quinidine, simple organic molecules generously provided by Nature, were the first compounds to be proposed to operate through a cooperative catalysis. To date, a full mechanistic characterization of the dual catalysis mode of cinchona alkaloids has proven a challenging objective, due to the transient, non-covalent nature of the involved catalyst,substrate interactions. Here, we propose a mechanistic rationale on how natural cinchona alkaloids act as efficient bifunctional catalysts by using a broad range of computational methods, including classical molecular dynamics, a mixed quantum mechanical/molecular mechanics (QM/MM) approach, and correlated ab-initio calculations. We also unravel the origin of enantio- and diastereoselectivity, which is due to a specific network of hydrogen bonds that stabilize the transition state of the rate-determining step. The results are validated by experimental evidence. [source] Synthesis of Novel Chiral and Acentric Coordination Polymers by the Reaction of Zinc or Cadmium Salts with Racemic 3-Pyridyl-3-aminopropionic AcidCHEMISTRY - A EUROPEAN JOURNAL, Issue 1 2004Zhi-Rong Qu Abstract Under hydrothermal (solvothermal) reaction conditions chiral compounds 1, 2, and 3 and one acentric compound 4 were obtained by the reaction of Zn2+ or Cd2+ with racemic 3-(3-pyridyl)-3-aminopropionic acid (rac -HPAPA). Compounds 1 and 2 crystallized in chiral space group P212121. At 105,°C, racemic 3-pyridyl-3-aminopropionic acid (rac -HPAPA) reacted with Zn(ClO4)2,6,H2O and dehydrogenated in situ to form the first chiral coordination polymer [Zn{(E)-3-C5H4NC(NH2)CHCOO}]ClO4 (1) with a ,-dehydroamino acid. Beyond 120,°C, the reaction of rac -HPAPA with Zn(ClO4)2,6,H2O deaminates in situ to form chiral coordination polymer [Zn{(E)-3-C5H4NCHCHCOO}(OH)] (2). At relatively low temperatures (70,°C), the solvothermal reaction of Zn(NO3)2,6,H2O with rac -HPAPA in methanol does not lead to any change in the ligand and results in the formation of a chiral (P212121) coordination polymer [Zn(papa)(NO3)] (3). The same reaction of Cd(ClO4)2,6,H2O with HPAPA also does not lead to any change in ligand and results in the formation of noncentric (Cc) coordination polymer [Cd(papa)(Hpapa)]ClO4,H2O (4). The network topology of both 1 and 3 is 10,3a, while 2 has a diamondoid-like (KDP-like, KDP=potassium dideuterophosphate) network. Particularly interesting from a topological perspective is that 4 has an unprecedented three-dimensional network. Compounds 1, 2, 3, and 4 are all second harmonic generation (SHG) active with 1 exhibiting the strongest response, while only 4 also displays good ferroelectric properties. [source] Molecular tweezers for enantiodiscrimination in NMR: Di-(R,R)-1-[10-(1-hydroxy-2,2,2-trifluoroethyl)-9-anthryl]-2,2,2-trifluoroethyl benzenedicarboxylates,CHIRALITY, Issue 6 2010Sergio Gil Abstract A series of new chiral molecular tweezers, di-(R,R)-1-[10-(1-hydroxy-2,2,2-trifluoroethyl)-9-anthryl]-2,2,2-trifluoroethyl phthalate (2), isophthalate (3) and terephthalate (4), were synthesized and their structure studied by NMR and molecular mechanics. Their effectiveness as chiral solvating agents for the determination of the enantiomeric purity of chiral compounds using NMR was demonstrated. Chirality 2010. © 2009 Wiley-Liss, Inc. [source] Determination of absolute configurations by X-ray crystallography and 1H NMR anisotropyCHIRALITY, Issue 5 2008Nobuyuki Harada Abstract To determine the absolute configurations of chiral compounds, many spectroscopic and diffraction methods have been developed. Among them, X-ray crystallographic Bijvoet method, CD exciton chirality method, and the combination of vibrational circular dichroism and quantum mechanical calculations are of nonempirical nature. On the other hand, X-ray crystallography using a chiral internal reference, and 1H NMR spectroscopy using chiral anisotropy reagents are relative and/or empirical methods. In addition to absolute configurational determinations, preparations of enantiopure compounds are strongly desired. As chiral reagents useful for both the preparation of enantiopure compounds by HPLC separation and the simultaneous determination of their absolute configurations, we have developed camphorsultam dichlorophthalic acid (CSDP acid) for X-ray crystallography and 2-methoxy-2-(1-naphthyl)propionic acid (M,NP acid) for 1H NMR spectroscopy. In this review, the principles and applications of these X-ray and NMR methods are explained using mostly our own data. Chirality, 2008. © 2007 Wiley-Liss, Inc. [source] Enantiomeric separation of imidazolinone herbicides using chiral high-performance liquid chromatographyCHIRALITY, Issue 3 2007Kunde Lin Abstract Chiral high-performance liquid chromatography (HPLC) is one of the most powerful tools to prepare enantiopure standards of chiral compounds. In this study, the enantiomeric separation of imidazolinone herbicides, i.e., imazethapyr, imazapyr, and imazaquin, was investigated using chiral HPLC. The enantioselectivity of Chiralpak AS, Chiralpak AD, Chiralcel OD, and Chiralcel OJ columns for the three analytes was compared under similar chromatographic conditions. Chiralcel OJ column showed the best chiral resolving capacity among the test columns. The resolved enantiomers were distinguished by their signs of circular dichroism detected at 275 nm and their structures confirmed with LC-mass spectrometric analysis. Factors affecting the chiral separation of imidazolinones on Chiralcel OJ column were characterized. Ethanol acted as a better polar modifier than the other alcohols including 2-propanol, 1-butanol, and 1-pentanol. Although the acidic modifier in the mobile phase did not influence chiral recognition, it was necessary for reducing the retention time of enantiomers and suppressing their peak tailing. Thermodynamic evaluation suggests that enantiomeric separation of imidazolinones on Chiralcel OJ column is an enthalpy-driven process from 10 to 40°C. This study also shows that small amounts of pure enantiomers of imidazolinones may be obtained by using the analytical chiral HPLC approach. Chirality 19, 2007. © 2006 Wiley-Liss, Inc. [source] Enthalpy change on mixing a couple of S - and R -enantiomers of some chiral compounds at 298.15 KCHIRALITY, Issue 8 2006Takayoshi Kimura Abstract Enthalpy change on the mixing of R - and S -enantiomers of chiral liquid compounds such as dimethyl malate (1), methyl 3-hydroxylbutanoate (2), 2-butanol (3), ethyl 4-chloro-3-hydroxylbutanoate (4), 1,3,3-trimethylbicycle-[2.2.1]heptan-2-one (5), 3,7-dimethyl-6-octenal (6), and 8-bromo-2,6-dimethyl-2-octene (7) is measured over the entire range of mole fractions at 298.15 K, albeit very small values. The mixing of chiral liquids of R - 1 + S - 1, R - 2 + S - 2, R - 3 + S - 3, R - 6 + S - 6, and R - 7 + S - 7 produces enthalpic destabilization over the entire range of mole fractions, while that of R - 4 + S - 4 and R - 5 + S - 5 shows enthalpic stabilization over entire compositions. Enthalpy change on mixing at an equimolar concentration and the intermolecular interaction obtained by the molecular mechanics calculations show a linear correlation, except for a few compounds measured. Chirality, 2006. © 2006 Wiley-Liss, Inc. [source] | |||||||||||||||||||||||||