Synthesis and characterization of phenanthrene derivatives with anticancer property against human colon and epithelial cancer cell lines

A variety of polycyclic aromatic hydrocarbons have been synthesized and structurally characterized in our laboratory. Phenanthrene derivatives were efficiently prepared in excellent yields and high purity via a two-step sequence. Heck coupling yielded the corresponding diarylethenes, followed by classical oxidative photocyclization to achieve the expected phenanthrenes. First, we envisioned to synthesize a variety of substituted phenanthrenequinones. Second, we investigated the possibility of a dibenz[a,c]phenazine formation by addition of o-phenylenediamine after completion of the oxidation process. Moreover, because phenanthrenequinones are available so simply, it is likely that other uses will be found for these compounds. For example, 9,10-phenanthrenequinone can be sequentially reduced, alkylated, acetylated, and sulfonated. All the synthesized derivatives were evaluated for cytotoxic activity in vitro against the human epidermoid carcinoma epithelial cells Hep-2 and human colon carcinoma cells Caco-2 using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. From the structure–activity point of view, position and nature of the electron donating and electron withdrawing functional groups attached to the phenanthrene skeleton may contribute to the anticancer action. Interestingly, the analysis of the IC₅₀ values suggests that most compounds exerted cytotoxic effects with selectivity against both cancer cells. Among them, methyl 8-methyl-9,10-phenanthrenequinone-3-carboxylate 11d showed the highest potency with IC₅₀ values of 2.81 and 0.97 μg/mL.     

Synthesis and resolution of a new thiahexahelicene

A new thiahexahelicene bearing a methoxy group, at a selected position on the terminal aromatic ring, was prepared in a good yield through Heck coupling and photocyclization reactions. The X-ray crystal structure of the product indicates that its conformation closely resembles that of the unsubstituted hexahelicene, whose idealized symmetry is C₂. Both enantiomers of the new helically chiral hexacyclic system have been successfully separated using (R)-2-phthalimidopropanoic acid chloride as a chiral resolving agent.     

Synthesis of carbazole derived aza[7]helicenes

Synthesis of four derivatives of symmetrical aza[7]helicenes is achieved by I₂-THF mediated photocyclization of corresponding bis-styryl derivatives. The cyclization furnished the desired angularly fused aza-helicene in moderate yields. The structures are established by NMR spectroscopy and single crystal X-ray analysis for the difluoro derivative. The series of synthesized aza[7]helicenes showed remarkable thermal stability as indicated by DSC analysis.     

Synthesis and characterization of new hexahelicene derivatives

The synthesis and structural characterization of a new hexahelicene derivative 2 is reported. This compound features a new type of structure bearing a bromine atom and a methoxy group. Suitable crystals of the latter indicate that its conformation closely resembles that of the unsubstituted [6]helicene, whose idealized symmetry is C2. This 3-bromo-14-methoxyhexahelicene was subjected to lithiation/phosphinilation and yielded the new 3-methoxy-14-(diphenylphosphino)hexahelicene 3.     

Synthesis,X-ray analysis and photophysical properties of a new N-containing pentacyclic helicene

A new helically chiral pentacyclic system containing one pyrrole ring was prepared in a good yield and purity via a three-step sequence involving Heck coupling and classical oxidative photocyclization. X-ray crystal structure analysis indicated that the conformation resembled that of unsubstituted pentahelicene, the idealized symmetry of which is C₂. The optical properties of the pentacyclic helicene were investigated and show interesting behaviour.     

Monoaza[5]helicenes. Part 2: Synthesis, characterisation and theoretical calculations

The synthesis of four different monoaza[5]helicenes is reported, to complete the whole series of these compounds, so that systematic studies on their properties can be carried out. They were fully characterised via NMR. A theoretical approach to explain why ring closure occurs to give the most crowded compound is reported, in comparison with earlier calculation methods.     

Asymmetric Synthesis of Overcrowded Alkenes by Transfer of Axial Single Bond Chirality to Axial Double Bond Chirality

Optically active overcrowded alkenes were synthesized by employing bis-β-naphthol as a chiral template during an intramolecular coupling reaction. The major isomer 2 has a unique helical structure with twisted and folded structural moieties. Removal of the chiral template afforded overcrowded thioxanthylidene 3 with 96 % ee, which indicates that no racemization or isomerization of the enantiomers took place.     

Synthesis and characterisation of a new helically chiral ruthenium complex

A new helically chiral hexacyclic phosphine, containing one thiophene ring was prepared in good yield via a five-step sequence involving a palladium-catalysed Mizoroki-Heck coupling reaction and classical oxidative photocyclisation. A mononuclear air stable ruthenium complex of this phosphine was also prepared and characterised.     

Stereoselective Synthesis of Coordination Compounds: Self-Assembly of a Polymeric Double Helix with Controlled Chirality

Its information content is infinitely smaller than that of DNA, but its structure (see picture) ressembles the double-stranded helix produced by nature. This self-assembled, configurationally predetermined coordination polymer is built up from enantiopure chiral bipyridine-type ligands and silver ions.     

Synthesis and resolution of 2-(diphenylphosphino)heptahelicene

Palladium catalysed Heck couplings have been applied to the two-step synthesis of a stilbene derivative bearing a diphenylphosphine oxide function which represents a suitable precursor for the photochemical generation of the corresponding [7]-helicene. After reduction of the phosphine oxide, resolution of the monodentate helical phosphine has been performed by means of the ortho-metallated (R)-1-(naphthyl)ethylamine-palladium complex. A ruthenium complex of (heptahelicen-2-yl)diphenylphosphine has also been prepared and fully characterized.     

Synthesis, photophysics and electroluminescence of new vinylene-copolymers with 2,4,6-triphenylpyridine kinked segments along the main chain

Two new vinylene alternating copolymers F and C that contained 2,4,6-triphenylpyridine as a common moiety and fluorene or carbazole, respectively, as an alternating moiety were prepared by Heck coupling. They showed an outstanding thermal stability being stable up to approximately 350 °C and had relatively high glass transition temperatures (140 and 111 °C). The existence of the 2,4,6-triphenylpyridine kinked units along the polymer backbone caused a partial interruption of the π-conjugation. The copolymers emitted blue-green light with emission maximum at 446-464 nm and quantum yields of 0.52 and 0.28 in THF solution. The electrochemical properties of copolymers F and C, including HOMO and LUMO levels, were estimated from their cyclic voltammograms. Their electroluminescence (EL) emission maxima (greater than 500 nm) showed significant red-shifts relative to the PL maxima, which has been explained by the direct cross recombination transition between electrons and holes trapped on carbazole or triphenylpyridine subunits. Moreover, the emission colors transform gradually with increasing bias and approach to white color at about 30 ∼ 35 V. The maximal luminance (maximal luminance efficiency) of the EL devices (ITO/PEDOT:PSS/F or C/Ca/Al) were 647 cd/m² (0.13 cd/A) or 615 cd/m² (0.10 cd/A), respectively.     

A Chiral Molecular Based Metamagnet Prepared from Manganese Ions and a Chiral Triplet Organic Radical as a Bridging Ligand

Below 5.4 K the one-dimensional polymeric complex made up of manganese(II ) hexafluoroacetylacetonate units and bridging bisaminooxylbenzene diradicals (shown in the picture) behaves as a metamagnet. The R-helical chain not only contains an S-configured chiral carbon center, but also an R-configured C₂-symmetric chiral skeleton of the organic ligand.     

Crystal Structures of Chiral Diastereoisomers of a Carbon-Based High-Spin Molecule

A chiral organic compound that displays magnetic properties has been synthesized for the first time. Two diastereomers of a molecule having an S=3/2 spin state have been characterized by X-ray crystal structure analysis (one of the diastereomers is shown in the space-filling model on the right). Optical resolution of one pair of stereoisomers was possible by chiral stationary phase HPLC.     

Recent progress on multidimensional construction of helicenes

Helicenes with unique π-conjugated helical structure and excellent chiroptical properties have received more and more attention. In this review, the idea of multidimensional construction of helicenes and their derivatives was proposed, and the related recent progress was summarized comprehensively.     

Conformational studies on peptides having chiral five-membered ring amino acid with two azido or triazole functional groups within the sequence of Aib residues

The chiral cyclic α,α-disubstituted α-amino acid, (3R,4R)-1-amino-3,4-diazido-1-cyclopentanecarboxylic acid [(R,R)-Ac₅c^dN3], was introduced into achiral α-aminoisobutyric acid (Aib) peptides. The azido groups of (R,R)-Ac₅c^dN3 in the peptides were efficiently converted into 1,2,3-triazole functional groups. FTIR, ¹H NMR, and CD spectra revealed that the dominant conformations of all peptides in solution were 3₁₀-helical structures without controlling the helical-screw sense. X-ray crystallographic analyses of peptides containing (R,R)-Ac₅c^dN3 showed that both the right-handed (P) and left-handed (M) 3₁₀-helical structures were present in the crystal state.     

Helical Coordination Polymers with Large Chiral Cavities

A quarter of the unit cell volume of [{Ni(4,4′‐dipy)(3‐nitrobenzoate)₂(MeOH)₂}_n], which crystallizes in the form of helices, is occupied by large chiral cavities (400–500 ų). The cavities are capable of encapsulating not only single molecules, but also face‐to‐face dimers of nitrobenzene (see stick model). 4,4′‐dipy=4,4′‐bipyridine.     

Predetermined Chirality at Metal Centers

Asymmetric synthesis in coordination chemistry was described very clearly by Smirnoff in 1920, but, contrary to the development in organic chemistry, it was almost completely neglected for several decades. The interest in chirality in coordination chemistry (see the stereoview of [Ru(bpy)₃]²⁺) has increased rapidly in recent times as a consequence of developments in several fields where chirality is important (polynuclear systems, supramolecular structures, and enantioselective catalysis). Here we show many examples of how, through the choice of ligand, the configuration of a metal center or the chirality of a helicate can be predetermined.