Asymmetric epoxidation of unfunctionalized alkenes catalyzed by sugar moiety-modified chiral salen-Mn(III) complexes

Several chiral Schiff-base ligands with sugar moieties at C-3 (3′) or C-5 (5′) of salicylaldehyde were synthesized from reaction of salicylaldehyde derivatives with diamine. These ligands coordinated with Mn(III) to afford the corresponding chiral salen-Mn(III) complexes characterized by FT-IR, MS, and elementary analysis. These complexes were used as catalysts for the asymmetric epoxidation of unfunctionalized alkenes. Only weak enantioselectivity is induced by the chiral sugar moieties at C-3 (3′) or C-5 (5′) in the case of absence of chirality in the diimine bridge moiety. It was also shown that the sugars at C-5 (5′) having the same rotation direction of polarized light as the diimine bridge in the catalyst could enhance the chiral induction in the asymmetric epoxidation, but the sugars with the opposite rotation direction would reduce the chiral induction.     

Nonhanded chirality in octahedral metal complexes

Chiral molecules can either be handed (i.e., "shoes") or nonhanded ("potatoes"). The only chiral ligand partition for tetrahedral metal complexes (or for a tetrahedral carbon atom such as that found in amino acids and other chiral biological molecules) is the fully unsymmetrical degree 6 partition (1(4)), which leads to handed metal complexes of the type MABCD with a lowest-degree chirality polynomial consisting of the product of all six possible linear factors of the type (s(i)-s(j)) where 1 < or = i,j < or = 4. The lowest-degree chiral ligand partitions for octahedral metal complexes are the degree 6 partitions (31(3)) and (2(3)) leading to handed chiral metal complexes of the types fac-MA(3)BCD and cis-MA(2)B(2)C(2). The form of the lowest-degree chirality polynomial for the (31(3)) chiral ligand partition of the octahedron resembles that of the (1(4)) chiral ligand partition of the tetrahedron, likewise with four different ligands. However, the form of the lowest-degree chirality polynomial for the (2(3)) chiral ligand partition of the octahedron corresponds to the square of the chirality polynomial of the (1(3)) chiral ligand partition of the polarized triangle, which likewise has three different ligands. Ligand partitions for octahedral metal complexes such as (2(2)1(2)), (21(4)), and (1(6)), which are less symmetrical than the lowest-degree chiral ligand partitions (31(3)) and (2(3)), lead to chiral octahedral metal complexes which are nonhanded. In such complexes, pairs of enantiomers can be interconverted by simple ligand interchanges without ever going through an achiral intermediate.     

Oxidative kinetic resolution of 1-phenylethanol catalyzed by sugar-based salen-Mn(III) complexes

Three new chiral salen-Mn(III) complexes with sugars at the C-5(5') positions of the salicylaldehyde moieties of the salen ligand were synthesized. Their structures were characterized by FTIR, MS, and elemental analysis. The complexes together with two previously reported ones were successfully used as chiral catalysts for the oxidative kinetic resolution (OKR) of 1-phenylethanol using PhI(OAc)2 as an oxidant and KBr as an additive. Excellent enantiomeric excess (up to 89%) of the product was achieved in 0.5h at 20 degrees C. The results showed that the sugars at C-5(5') of salicylaldehyde moieties in the ligand had influences on the catalytic performances of the complexes. It was concluded that the sugars with the same rotation direction of polarized light as the diimine bridge within the complex could enhance the chiral induction of the complex in the OKR of 1-phenylethanol, but the sugars with the opposite one would reduce that of the corresponding complex.     

Circular dichroism of surface complexes based on quantum dots and azo dye

Chiral properties of surface complexes based on CdSe/ZnS quantum dots (QDs) and 1‐(2‐pyridylazo)‐2‐naphthol (PAN) azo dye were investigated by circular dichroism spectroscopy. The use of L‐, D‐cysteine (Lcys, Dcys) capping ligands allowed us to obtain water‐soluble chiral QD‐PAN complexes. The characterization of the complexes was performed by UV‐vis, FTIR, and CD spectroscopy. Quantum chemical TDDFT calculated CD spectra reproduced the experimentally observed sign patterns, which originate from binding Lcys or Dcys and PAN molecules to the same Zn atom on the QD surface. The resulting complex is characterized by a large circular dichroism in comparison with an ordinary QD chirality induced by cysteine molecules. The pattern of CD signal is the same for Lcys and Dcys ligands in chiral QD‐PAN complex.     

Circularly polarized luminescence studies of the adducts formed with Eu(III) β-diketone complexes and (—)-sparteine

The optical activity resulting from the complexation of (—)-sparteine by a series of Eu(III) β-diketone compounds has been studied by means of circularly polarized luminescence spectroscopy. It was found that the presence of at least one perfluoro group was necessary for the formation of an adduct complex. With Eu(III) complexes containing achiral β-diketone ligands, it was found that the observed chirality could be considered to result from a combination of vicinal and conformational effects. With Eu(III) complexes containing chiral β-diketone ligands, the optical activity was found to be dominated by confïgurational effects.     

Cyclomaltooligosaccharide-assisted spectroscopic discrimination of phthalimido-derived amino acids through the formation of molecular aggregates

Spectroscopic evidence was used to demonstrate the formation of molecular associates in an aqueous solution of phthalimido tryptophan. These molecular associates are loosely formed through pi-pi aromatic stacking, properties that are not sufficient to cause NMR spectroscopic enantiomeric discrimination. A cyclomaltooligosaccharide with a larger cavity, such as cyclomaltooctaose (gamma-cyclodextrin), is capable of forming a ternary complex with these molecular associates and enhances pi-pi aromatic stacking interactions, resulting in NMR enantiomeric discrimination. Electrospray-ionization mass spectroscopy (ESIMS) and NOESY two-dimensional NMR spectroscopic methods were used to study these complexes. Association constants and thermodynamic data for these cyclomaltooligosaccharide complexes were also estimated.     

Effect of chirality,length and diameter of carbon nanotubes on the adsorption of 20 amino acids: a molecular dynamics simulation study

We carried out molecular dynamics simulations to study the adsorption of all the 20 amino acids (AAs; aromatic, polar and non-polar) on the surface of chiral, zigzag and armchair single-walled carbon nanotubes. The adsorption was occurring in all systems. In the aromatic AAs, the π–π stacking and the semi-hydrogen bond formation cause a strong interaction with the carbon nanotubes (CNTs). We also investigated the chirality, length and diameter dependencies on adsorption energies. We found that all AAs have more tendency to adsorption on the chiral and zigzag CNTs over the armchair. The results show that increasing both the diameter and the length causes the enhancement of the adsorption energy. But, the effect of the length is more than of the diameter. For example, the adsorption energy of Trp on the surface of CNT (4,1), with 2 nm length, is 20.4 kcal/mol. When the length of CNT becomes twice, the adsorption energy increases by 24 ± 0.3%. But by doubling the diameter, the adsorption energy increased only by 9.8 ± 0.25%.     

Chirality as a tool in nucleic acid recognition: principles and relevance in biotechnology and in medicinal chemistry

The understanding of the interaction of chiral species with DNA or RNA is very important for the development of new tools in biology and of new drugs. Several cases in which chirality is a crucial point in determining the DNA binding mode are reviewed and discussed, with the aim of illustrating how chirality can be considered as a tool for improving the understanding of mechanisms and the effectiveness of nucleic acid recognition. The review is divided into two parts: the former describes examples of chiral species interacting with DNA: intercalators, metal complexes, and groove binders; the latter part is dedicated to chirality in DNA analogs, with discussion of phosphate stereochemistry and chirality of ribose substitutes, in particular of peptide nucleic acids (PNAs) for which a number of works have been published recently dealing with the effect of chirality in DNA recognition. The discussion is intended to show how enantiomeric recognition originates at the molecular level, by exploiting the enormous progresses recently achieved in the field of structural characterization of complexes formed by nucleic acid with their ligands by crystallographic and spectroscopic methods. Examples of application of the DNA binding molecules described and the role of chirality in DNA recognition relevant for biotechnology or medicinal chemistry are reported.     

The chirality selectivity in the uptake of platinum (II) complexes with 1,2-cyclohexanediamine isomers as carrier ligand by human erythrocytes

The uptake kinetics of cisplatin analogs of 1,2-cyclohexanediamine(dach) isomers with various leaving groups, by human erythrocytes in plasma isotonic buffer, were studied. The experimental results showed that the uptake rate constants (k values) decrease with the change of leaving group in the sequence: chloride (Cl) > squaric acid (SA) > oxalate (OX) > demethylcantharic acid (DA), with the same dach isomer as carrier group. It is noteworthy that for the platinum (II) complexes with the same leaving group, the k values always reduce as: 1R, 2R-dach > 1R, 2S-dach > 1S, 2S-dach. This result reflects the chirality selectivity. No differences in reactivity to protein thiols and effects on membrane permeability were found for the R,R-, R,S-, S,S-isomeric complexes. It is proposed that the chirality selectivity in uptake is due to the recognition of the chirality of the platinum complexes by the erythrocyte membrane. The interactions between the chiral platinum complexes and the head groups of the membrane phospholipid molecules are probably involved.     

Porphyrins and metalloporphyrins: versatile circular dichroic reporter groups for structural studies

During the last few years, porphyrins and metalloporphyrins have attracted widespread attention as chromophores for studies in circular dichroism (CD), an indispensable chiroptical tool for monitoring chiral interactions. This review summarizes the multifaceted properties of porphyrins and metalloporphyrins, powerful CD chromophores that are characterized by their intense and red-shifted Soret band, propensity to undergo pi-pi stacking, facile incorporation of metals, and ease in varying solubility. Such attributes make porphyrins one of the most attractive and sensitive chromophores used in CD studies. They offer possibilities for studying the stereochemistry of chiral porphyrin assemblies, large organic molecules, biopolymers, and compounds available in miniscule quantities. The tendency of porphyrins to undergo pi-pi stacking and zinc porphyrins to coordinate with amines enable the CD exciton chirality method to be extended to configurational assignments of flexible compounds containing only one stereogenic center. Various artificial porphyrin receptors have been synthesized for the recognition of biologically important chiral guests such as carbohydrates, amino acids, and their derivatives. The induced CD of the host porphyrin Soret band reflects the identity of guests and binding modes of host/guest complexation with high sensitivity.     

Spiral galaxies as enantiomers: Chirality,an underlying feature in chemistry and astrophysics

Spiral galaxies are axisymmetric objects showing 2D chirality when projected onto a plane. Features in common with tetrahedral molecules are pointed out, in particular the existence of a preferred chiral modality for genetic galaxies as in amino acids and sugars. Environmental effects can influence the intrinsic chirality of originally isolated stellar systems so that a progressive loss of chirality is recognized in the Hubble morphological sequence of galaxies. © 2005 Wiley‐Liss, Inc. Chirality     

Chirality in Distorted Square Planar Pd(O,N)2 Compounds

Salicylidenimine palladium(II) complexes trans‐Pd(O,N)₂ adopt step and bowl arrangements. A stereochemical analysis subdivides 52 compounds into 41 step and 11 bowl types. Step complexes with chiral N‐substituents and all the bowl complexes induce chiral distortions in the square planar system, resulting in Δ/Λ configuration of the Pd(O,N)₂ unit. In complexes 1 , 2 , 3 , 4 , 5 , 6 with enantiomerically pure N‐substituents ligand chirality entails a specific square chirality and only one diastereomer assembles in the lattice. Dimeric Pd(O,N)₂ complexes with bridging N‐substituents in trans‐arrangement are inherently chiral. For dimers 7 , 8 , 9 , 10 , 11 different chirality patterns for the Pd(O,N)₂ square are observed. The crystals contain racemates of enantiomers. In complex 12 two independent molecules form a tight pair. The (R_C) configuration of the ligand induces the same Δ chirality in the Pd(O,N)₂ units of both molecules with varying square chirality due to the different crystallographic location of the independent molecules. In complexes 13 and 14 atrop isomerism induces specific configurations in the Pd(O,N)₂ bowl systems. The square chirality is largest for complex 15 [(Diop)Rh(PPh₃)Cl)], a catalyst for enantioselective hydrogenation. In the lattice of 15 two diastereomers with the same (R_C,R_C) configuration in the ligand Diop but opposite Δ and Λ square configurations co‐crystallize, a rare phenomenon in stereochemistry. Chirality 25:663–667, 2013. © 2013 Wiley Periodicals, Inc.     

The enduring legacy of Koji Nakanishi's research on natural products and bioorganic chemistry. Part 2. Inception and establishment of the ECD exciton chirality method in 1960s to 1970s: A marvel of Nakanishi's Japanese team

The electronic circular dichroism (ECD) exciton chirality method is very useful for determining the absolute configuration (AC) of chiral compounds. In the ECD spectroscopy, the chromophore-chromophore interaction, ie, exciton coupling, is very important. For example, Harada and Nakanishi first discovered in 1969 that chiral dibenzoates exhibit exciton split bisignate Cotton effects, from the sign of which the screw sense between two long axes of benzoate chromophores, ie, the AC of dibenzoate, can be determined. This method was named the dibenzoate chirality rule and has been successfully applied to various natural products to determine their ACs. During these studies, it was also found that this CD method was expanded to encompass other aromatic and olefin chromophores like naphthalene, diene, enone, etc. Therefore, the name of the dibenzaote chirality rule was changed to the CD exciton chirality method. In 1970s, there were heated controversies about the inconsistency between X-ray Bijvoet and CD exciton chirality methods, which was a shocking and serious problem in the community of molecular chirality research. Harada and coworkers synthesized the most ideal cage compound with two anthracene chromophores to connect X-ray Bijvoet and CD exciton chitality methods and proved that these two methods are consistent with each other.     

Optically active porous hybrid particles constructed by alkynylated cellulose nanocrystals,helical substituted polyacetylene,and inorganic silica for enantio-differentiating towards naproxen

This article reports on a novel type of ternary chiral porous hybrid particles (TCPHPs) constructed by alkynylated cellulose nanocrystals (A-CNCs), helical substituted polyacetylene, and inorganic silica. The resulting TCPHPs combine the respective advantages of the three components. A-CNCs serve as stabilizer, co-monomer, and chiral source simultaneously and transfer their chirality to the resulting helical substituted polyacetylenes in the course of copolymerization with achiral acetylenic monomer following “sergeants and soldiers rule”. Helical substituted polyacetylenes form chiral helical structures and thus endow TCPHPs with the anticipated optical activity. Inorganic silica constitutes the rigid framework and is covalently bonded with the organic components through hydrolysis of Si-O-Et groups. Phase separation between the organic and inorganic components renders TCPHPs with abundant pores. Scanning electron microscope (SEM) images confirm the formation of spherical particles with porous structures. Circular dichroism spectra demonstrate the optical activity of the chiral hybrid particles. The as-prepared TCPHPs exhibit capacity for enantio-differentiating performance towards chiral naproxen.     

Corolla chirality does not contribute to directed pollen movement in Hypericum perforatum (Hypericaceae): mirror image pinwheel flowers function as radially symmetric flowers in pollination

Corolla chirality, the pinwheel arrangement of petals within a flower, is found throughout the core eudicots. In 15 families, different chiral type flowers (i.e., right or left rotated corolla) exist on the same plant, and this condition is referred to as unfixed/enantiomorphic corolla chirality. There are no investigations on the significance of unfixed floral chirality on directed pollen movement even though analogous mirror image floral designs, for example, enantiostyly, has evolved in response to selection to direct pollinator and pollen movement. Here, we examine the role of corolla chirality on directing pollen transfer, pollinator behavior, and its potential influence on disassortative mating. We quantified pollen transfer and pollinator behavior and movement for both right and left rotated flowers in two populations of Hypericum perforatum. In addition, we quantified the number of right and left rotated flowers at the individual level. Pollinators were indifferent to corolla chirality resulting in no difference in pollen deposition between right and left flowers. Corolla chirality had no effect on pollinator and pollen movement between and within chiral morphs. Unlike other mirror image floral designs, corolla chirality appears to play no role in promoting disassortative mating in this species.     

Unfolding and refolding of bovine serum albumin induced by cetylpyridinium bromide

The interaction of bovine serum albumin (BSA) with cationic surfactant cetylpyridinium bromide (CPB) in aqueous solution (pH 7.00) was studied quantitatively with ultraviolet (UV)-visible, far-UV, and near-UV circular dichroism, fluorescence, small angle x-ray scattering, and nuclear magnetic resonance measurement. It was found that CPB at low and high concentrations could induce the unfolding and refolding of BSA, respectively. We suggest that in the unfolding process, there existed BSA-CPB complex with the "necklace and bead" structure in which the unfolded BSA wrapped around CPB micelles, and that the hydrophobic interaction between the complexes led to the formation of large aggregates. The aromatic headgroup of CPB interacted with the tryptophan residues of BSA, resulting in the aromatic ring stacking between BSA and CPB. During the refolding process, the BSA molecule was penetrated into the rod micelle of CPB and the hydrophobic moiety of the BSA molecule was exposed outside while its hydrophilic part was hidden inside, thereby disrupting the aromatic ring stacking.     

Alleviation of mutagenic effects of polycyclic aromatic agents (quinacrine mustard, ICR-191 and ICR-170) by caffeine and pentoxifylline

Previous studies performed by others indicated that apart from its other biological effects, caffeine (CAF) may have a role in protection of organisms against cancer. However, biological mechanism of this phenomenon remained unknown. Recent studies suggested that caffeine can form stacking (pi-pi) complexes with polycyclic aromatic chemicals. Therefore, one might speculate that effective concentrations of polycyclic aromatic mutagens could be reduced in the presence of caffeine. Here we demonstrate that caffeine and another xanthine, pentoxifylline (PTX), effectively alleviate mutagenic action of polycyclic aromatic agents (exemplified by quinacrine mustard (QM), 2-methoxy-6-chloro-9-(3-(2-chloroethyl)aminopropylamino)acridine.2HCl (ICR-191) and 1,3,7-propanediamine-N-(2-chloroethyl)-N'-(6-chloro-2-methoxy-9-acridinyl)-N-ethyl.2HCl (ICR-170)), but not of aliphatic mutagens (exemplified by mechlorethamine), in the recently developed mutagenicity test based on bacterium Vibrio harveyi. Biophysical studies indicated that caffeine and pentoxifylline can form stacking complexes with the aromatic agents mentioned above. Molecular modeling also confirmed a possibility of stacking interactions between examined molecules.     

Synthesis of soluble aromatic multilayered tetra(m-phenylurea) and analysis of its helical conformation in various solvents

Aromatic N,N'-dimethylated urea exists in (cis, cis) form, both in the crystal and in solution, and this structure can be utilized to construct intramolecular aromatic multilayered oligomers. These structures show helical conformation with all-R or all-S axis chirality, when the benzene rings are connected at the meta positions. To investigate the dynamic conformational behavior of such aromatic multilayered ureas in various solvents, we synthesized tetra(m-phenylurea) 3 bearing two chiral N-2-(methoxyethoxyethoxy)propyl groups and six N-methoxyethoxyethyl groups. The high solubility of compound 3 enabled its analysis in various solvents, including water. The CD spectra of compound 3 showed broad electronic absorption with high temperature-dependency, owing to the induction of handedness, in acetonitrile, chloroform, and methanol. In water, the CD signals of compound 3 indicated the presence of similar helical structure, but temperature-dependency was not observed.     

Enantiopure platinum(II) complexes with chiral diphosphine and diphosphinite ligands derived from 2,2-biphosphole: Synthesis, crystal structure and catalysis

Enantiopure platinum(II) complexes have been synthetized with chiral stereodynamic diphosphine and diphosphinite ligands derived from 2,2-biphosphole through a dynamic chirality control upon coordination. Catalytic performances of these platinum complexes have been explored in asymmetric hydroformylation. All complexes proved to be effective catalysts with respect to chemoselectivity and regioselectivity but induced only low enantioselectivities.     

The use of circular dichroism spectroscopy for studying the chiral molecular self-assembly: an overview

Self-assembly plays an important role in the formation of many chiral biological structures and in the preparation of chiral functional materials. Therefore the control of chirality in synthetic or biological self-assembled systems is important either for the comprehension of recognition phenomena or to obtain materials with predictable and controllable properties. Circular dichroism was developed to study molecular chirality, however, because of its outstanding sensitivity to chiral perturbations of the system under investigation; it has been extended more recently to supramolecular chemistry. In particular, self-assembly processes leading to the formation of chiral supramolecular architectures (and eventually to gels or liquid crystal phases) can be monitored by CD. Furthermore, CD spectroscopy often allows one to obtain structural information on the assembled structures. This review deals with representative contributions to the study of supramolecular chirality by means of circular dichroism.