Enantioseparation using alkoxyphenylcarbamates of cellulose and amylose as chiral stationary phase for high-performance liquid chromatography

Cellulose and amylose phenylcarbamates having one or two alkoxy groups on a phenyl ring were synthesized, and their chiral recognition abilities as chiral stationary phases for HPLC were evaluated. Compared to the 4-methoxyphenylcarbamates of cellulose and amylose, which are known to show a poor chiral recognition, the 3-methoxyphenylcarbamates exhibited much higher chiral recognitions. For cellulose derivatives, as the bulkiness of the 3-alkoxy group increased, the chiral recognition ability increased. On the other hand, for the amylose derivatives, a clear relation between the chiral recognition and the bulkiness of the alkoxy group was not observed, and the 3-methoxy, ethoxy, and isopropoxyphenylcarbamates showed relatively high chiral recognitions. The introduction of two methoxy groups to the meta-positions decreased the chiral recognition ability. In order to discuss the relationship between the structure and chiral recognition ability of the alkoxyphenylcarbamates, their molecular models were constructed.     

Two modes of asymmetric polymerization of phenylacetylenes having an L‐amino alcohol residue and two hydroxy groups

Four novel chiral phenylacetylenes having an L ‐amino alcohol residue and two hydroxymethyl groups were synthesized and polymerized by an achiral catalyst ((nbd)Rh⁺[η⁶‐(C₆H₅)B^?(C₆H₅)₃]) or a chiral catalytic system ([Rh(nbd)Cl]₂/(S)‐ or (R)‐phenylethylamine ((S)‐ or (R)‐PEA)). The two resulting polymers having an L ‐valinol or L ‐phenylalaninol residue showed Cotton effects at wavelengths around 430 nm. This observation indicated that they had an excess of one‐handed helical backbones. Positive and negative Cotton effects were observed only for the polymers having an L ‐valinol residue produced by using (R)‐ and (S)‐PEA as a cocatalyst, respectively, although the monomer had the same chirality. Even when the achiral catalyst was used, the two resulting polymers having an L ‐valinol or L ‐phenylalaninol residue showed Cotton effects despite the long distance between the chiral groups and the main chain. We have found the first example of a new type of chiral monomer, that is, a chiral phenylacetylene monomer having an L ‐amino alcohol residue and two hydroxy groups that was suitable for both modes of asymmetric polymerization, that is, the helix‐sense‐selective polymerization ( HSSP ) with the chiral catalytic system and the asymmetric‐induced polymerization ( AIP ) with the achiral catalyst. The other two monomers having L ‐alaninol and L ‐tyrosinol were found to be unsuitable to neither HSSP nor AIP because of their polymers' low solubility. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

HPLC enantioresolution of (R,S)-baclofen using three newly synthesized dichloro-s-triazine reagents having amines and five others having amino acids as chiral auxiliaries

Enantioresolution of (R,S)-baclofen was accomplished using a newly synthesized set of three chiral derivatizing reagents (CDRs) having amines [(S)-(-)-α,4-dimethylbenzylamine, (-)-cis-myrtanylamine and (R)-(-)-1-cyclohexylethylamine] as chiral auxiliaries in cyanuric chloride and another set of five CDRs having amino acids (L-Leu, D-Phg, L-Val, L-Met and L-Ala) as chiral auxiliaries. These eight CDRs were used for synthesis of diastereomers of (R,S)-baclofen under microwave irradiation. The diastereomers were separated on a reversed-phase C(18) column using mixtures of methanol with aqueous trifluoroacetic acid with UV detection at 230 nm. Chromatographic data obtained for the two sets of diastereomers were compared among themselves and among the two groups. The method was validated for limit of detection, linearity, accuracy and precision.     

Chemical applications of topology and group theory. XXI: Chirality in transitive skeletons and qualitative completeness [1]

This paper unifies the following ideas for the study of chirality polynomials in transitive skeletons: (1) Generalization of chirality to permutation groups not corresponding to three-dimensional symmetry point groups leading to the concepts of signed permutation groups and their signed subgroups; (2) Determination of the total dimension of the chiral ligand partitions through the Frobenius reciprocity theorem; (3) Determination of signed permutation groups, not necessarily corresponding to three-dimensional point groups, of which a given ligand partition is a maximum symmetry chiral ligand partition by the Ruch-Schönhofer partial ordering, thereby allowing the determination of corresponding chirality polynomials depending only upon differences between ligand parameters; such permutation groups having the point group as a signed subgroup relate to qualitative completeness. In the case of transitive permutation groups on four sites, the tetrahedron and polarized square each have only one chiral ligand partition, but the allene and polarized rectangle skeletons each have two chiral ligand partitions related to their being signed subgroups of the tetrahedron and polarized square, respectively. The single transitive permutation group on five sites, the polarized pentagon, has a degenerate chiral ligand partition related to its being a signed subgroup of a metacyclic group with 20 elements. The octahedron has two chiral ligand partitions, both of degree six; a qualitatively complete chirality polynomial is therefore homogeneous of degree six. The cyclopropane (or trigonal prism or trigonal antiprism) skeleton is a signed subgroup of both the octahedron and a twist group of order 36; two of its six chiral ligand partitions come from the octahedron and two more from the twist group. The polarized hexagon is a signed subgroup of the same twist group but not of the octahedron and thus has a different set of six chiral ligand partitions than the cyclopropane skeleton. Two of its six chiral ligand partitions come from the above twist group of order 36 and two more from a signed permutation group of order 48 derived from the P₃[P ₂] wreath product group with a different assignment of positive and negative operations than the octahedron.     

New ferroelectric and antiferroelectric liquid crystalline materials containing differing numbers of lactate units

A new series of chiral liquid crystalline materials having the same rigid core containing a keto group, and various numbers of ( S )-lactate groups in the chiral segment, has been synthesized and studied. All the compounds contain a branched terminal alkyl chain derived from ( S )-2-methylbutanol. The influence of the number of lactate units on mesogenic behaviour has been studied. All the compounds show the paraelectric SmA phase and the ferroelectric SmC * phase over rather wide temperature ranges. The antiferroelectric SmC * A phase was observed for the compound possessing two lactate groups.     

Preparation of polysaccharide derivatives and their chiral recognition mechanism

Several new phenylcarbamate derivatives of cellulose and amylose having fluoro and methyl groups or 4-trimethylsilyl substituent on the phenyl groups were prepared and their chiral recognition abilities as chiral stationary phases for HPLC were evaluated. These derivatives are soluble in chloroform and exhibit chiral discrimination in ¹H NMR spectroscopy. Based on the above results and molecular mechanics calculation of interaction energies between the derivatives and enantiomers, the mechanism of chiral discrimination is discussed.     

Synthesis of enantiopure 1,2-diamine attached to cross-linked polystyrene and its application to an insoluble catalyst for asymmetric hydrogenation

A novel enantiopure 1,2-diamine (5) having two phenolic hydroxy groups was attached into chloromethylated polystyrene through benzyl ether linkage, which was used as a chiral ligand of the catalyst in asymmetric hydrogenation of acetophenone.     

COVALENTLY BONDING CHIRAL POLYURETHANE ON AMINATED SILICA GEL： A NEW STRATEGY TO PREPARE CHIRAL STATIONARY PHASE FOR HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

Two polyurethanes of different molecular weights were prepared by the copolymerization of phenyl diisocyanate and diisopropyl tartrate. The polyurethanes having terminal isocyanate groups were reacted with 3-aminopropyl silica gel to afford two chiral stationary phases. The Mn of the two polyurethanes were 4057 g/mol and 6442 g/mol. The polyurethanes and the corresponding chiral stationary phases were characterized by FT-IR, 1H NMR and elemental analysis. The loading capacities of the polyurethanes on silica gel were 0.68 mmol units/g and 0.61 mmol units/g, respectively. The separation performance and the influence of additives, triethylamine and trichloroacetic acid, on the separation of chiral compounds were investigated by HPLC. The chiral stationary phase prepared from polyurethane with Mn of 4057 g/mol demonstrated better enantioseparation capability than that with Mn of 6442 g/mol. Additionally, it was found that the addition of triethylamine and trichloroacetic acid in the mobile phases significantly improved the enantioseparation for these two chiral stationary phases.     

Synthesis of Chiral Crownophanes Having Two Phenolic Groups via Tandem Claisen Rearrangement and Their Chiral Recognition

Asymmetric crownophanes having a chiral binaphthyl unit and two phenolic hydroxyl groups were thermally synthesized from the corresponding macrocyclic ethers via tandem Claisen rearrangement. Circular dichroism (CD) spectroscopic studies and HPLC experiments confirmed that little racemization of these crownophanes occurred during the thermal rearrangement. The association constants for the interaction of the chiral crownophanes with the enantiomers of phenylethylamine, phenylglycinol, and phenylalaninol were determined by a ¹H NMR titration method in CD₂Cl₂. As a result, the 27 membered crownophane has some chiral recognition for phenylglycinol.     

Novel chiral porphyrins with C2 symmetry

Described is the preparation of chiral octaethylporphyrin derivatives having two 2-substituted naphthyl groups in a trans orientation at the 5- and 15-meso positions and formyl or hydroxymethyl or alkoxymethyl group derived therefrom at the 10-meso position. One of the derivatives has been successfully resolved into enantiomers by means of HPLC.     

New ferroelectric liquid crystalline materials containing one and two lactate groups attached to the molecular core

Several new liquid crystalline materials containing one, two or three chiral centres and having one or two lactate groups in the molecular core have been synthesized. Most of the materials show the blue phase, chiral nematic phase, paraelectric smectic A phase and orthogonal hexatic smectic B phase; some possess the ferroelectric SmC* phase. A study of the mesomorphic properties has been performed using differential scanning calorimetry, optical microscopy and X-ray diffraction. The thickness of the smectic layers and the value of the average distance between the long axes of neighbouring molecules were determined. In the SmC* phase, the temperature dependence of spontaneous polarization, spontaneous tilt angle and helical pitch was measured. The influence of the number of lactate groups on mesogenic behaviour has been established.     

Microstructures Based on Thermotropic Liquid-Crystalline Polymers in the Low Molar Mass Nematogenic 5CB

Summary: The unique characteristics of two polyacrylates having the same side chain chiral mesogenics groups and different spacer lengths allowed the stabilization of ordered polymer rich-phases in solution with the nematic solvent 5CB. These microstructures are smectic having fibrous-like and rode-like morphologies, in spite of the mesophases of the polymers in bulk. The interactions between the mesogenic groups in the polymer and the solvent 5CB stabilize the microstructures and leads to birefringence at temperatures above the 5CB clearing point. Polarized optical microscopy data are complemented by SAXS to fully describe the mesomorphic behavior of the mixtures.     

Synthesis and optical characterization of novel azacrown ethers containing an acridinone or an N-methylacridinone unit as potential fluorescent chemosensors

Four new achiral and four new chiral monoazacrown ethers containing an acridinone or an N-methylacridinone fluorescent signalling unit were prepared by reacting chloromethyl-substituted acridinone derivatives with achiral monoazacrown ethers with different cavity sizes and enantiopure monoaza-18-crown-6 ethers having two methyl and two isobutyl groups on their chiral centres, respectively. The operation of these chemosensors is based on the photoinduced electron transfer (PET) process, thus they show fluorescence enhancement in the presence of cationic guests. Their fluorescent behaviour as well as their complexation properties towards selected metal ions and the enantiomers of α-(1-naphthyl)ethylammonium perchlorate and potassium mandelate were examined.     

Highly Selective Molecular Recognition of Biologically Active Substances Using Liquid Phase Separation

 The development of new chiral stationary phases has been very important in the accurate analysis of drug enantiomers and their metabolites in biological samples during drug discovery and development. New chiral stationary phases have been developed usin     

Organocatalytic Enantioselective Nucleophilic Alkynylation of Allyl Fluorides Affording Chiral Skipped Ene‐ynes

Asymmetric methods for preparation of chiral alkynyl‐containing compounds are in extremely high demand in many sectors of chemical research. In this work, we report the discovery of a general organocatalytic enantioselective alkynylation based on the idea of Si/F activation of the allylic C?F bond. This approach features reasonably broad substrate scope, functional group tolerance, and relatively neutral, mild, and operationally convenient reaction conditions; all of which bode well for the synthetic value of the discovered method. In particular, this method provides unique chiral skipped 1,4‐ene‐ynes having two kinds of versatile functional groups.     

Chiral Amplification during Asymmetric‐Induced Copolymerization of Phenylacetylenes with Tight Cis‐Cisoidal Main Chains

A novel phenylacetylene ( 1 ) having two hydroxyl groups and a chiral pinanyl group together with the other three related phenylacetylenes has been synthesized and (co)polymerized by using an achiral catalytic system. Among the four monomers, only 1 is suitable to the asymmetric‐induced polymerization ( AIP ). Chiral amplification phenomenon is only observed in the copolymerization of 1 with an achiral phenylacetylene having two hydroxyl groups ( 3 ). The tight helical cis‐cisoidal main chain formed by making intramolecular hydrogen bonds between the hydroxyl groups in the copoly( 1 / 3 ) enhances the efficiency of chiral induction and as a result chiral amplification phenomenon is observed during the copolymerization.

     

"Click" post-synthetic modification of metal-organic frameworks with chiral functional adduct for heterogeneous asymmetric catalysis

Two enantiomeric Zn-MOFs, having l- or d-proline chiral functionality, were achieved through in situ click reactions by modifying two opposite chiral adducts within the same pre-assembled achiral MOFs, respectively. Both of them exhibited remarkable catalytic activities in the relative asymmetric aldol reactions, and led to the formation of opposite enantiomorphs. The significant advantage of this approach not only includes the conversion of chemically and thermally robust MOFs into enantiomeric chiral material having catalytically active sites, but also involves the potential applications in asymmetric transformations with desirable chiralities of a special enantiomorph.     

Development of chiral pincer palladium complexes bearing a pyrroloimidazolone unit. Catalytic use for asymmetric Michael addition

Novel pincer palladium complexes having chiral hexahydro-1H-pyrrolo[1,2-c]imidazolone groups were designed and prepared. Catalytic asymmetric Michael addition of isopropyl 2-cyanopropionate to ethyl vinyl ketone was catalyzed by the chiral pincer palladium complex to give isopropyl 2-cyano-2-methyl-5-oxoheptanoate with high enantioselectivity (up to 83% ee). [structure: see text]     

Mutarotation and isomerization of imines. Substituted N-(1-phenylethyl)-1-benzoylbenzylideneimines.

The mutarotation observed for several benzilmonoimines, having a chiral center, is atributed to the equilibration between two stereoisomers which differ in configuration around the single bond OCCN which, due to restricted rotation, becomes a chiral axis of the imines.     

New types of multifunctional liquid crystalline photochromic copolymers for optical data recording and storage

A new family of multifunctional chiral‐photochromic liquid crystalline (LC) copolymers containing mesogenic, chiral and photoactive groups were synthesized. The new principles of photo‐regulation of the helical supramolecular structure and optical properties of the binary and ternary chiral‐photochromic LC polymers based on the change of helical twisting power of the chiral‐photochromic monomer units, the dual photochromism and photochemical spectral gap burning were developed. It was shown, that the introduction of small amount of low‐molar‐mass chiral‐photochromic dopants in chiral LC copolymers having different helix signs followed by light irradiation permits one to twist or untwist the helical supramolecular structure. The synthesized polymers are shown to be promising candidates for colour data recording and storage.