Chlorine Substituents Research Articles

Electrochemical O-trifluoromethylation of electron-deficient phenols

A simple and sustainable one-step strategy for the preparation of electron-deficient aryl trifluoromethyl ethers (ArOCF3) from the corresponding phenols by electrochemical synthesis is presented. Anodic oxidation of trifluoromethane sulfinate (Langlois reagent) leads to direct O-trifluoromethylation of phenol-derivatives bearing fluorine, chlorine, bromine and nitrile substituents under mild conditions in yields up to 75% and in gram-scale. This electrochemical protocol provides an economic and green synthesis for an otherwise inaccessible class of molecules without the need for expensive or toxic reagents, oxidants or metal catalysts.

Microbial reductive dechlorination of polychlorinated dibenzo-p-dioxins: Pathways and features unravelled via electron density

Microbial reductive dechlorination provides a promising approach for remediating sites contaminated with polychlorinated dibenzo-p-dioxins (PCDDs). Nonetheless, the overall dechlorination pathways and features remain elusive. Herein, we address these issues by quantum chemical calculations, considering the calibrations of reductive dechlorination of 15 PCDDs mediated by three Dehalococcoides strains. Chlorine substituents with lower electron density are prone to be microbially abstracted, which differentiates 72 microbe-active PCDDs from 3 nonactive analogues with a success rate of 100%. For all 256 transformation routes of 75 PCDDs, electron density differences of chlorines pinpoint 105 viable and 125 unviable pathways, corresponding a success rate of 90%. The feasibility of 26 reductive dechlorination pathways are uncertain because of the limited available experimental data. 98% (251/256) of microbial chlorine abstraction follows an order of ClO,Cl>ClCl,Cl>ClH,O>ClH,Cl>ClH,H=0. PCDDs solely containing chlorines at C1, C4, C6, and/or C9 can be completely dechlorinated to non-chlorinated dioxin; while PCDDs housing chlorines at C2, C3, C7, and/or C8 can be dechlorinated to 2-MCDD or 2,7/8-DCDD as final products. These findings also support reductive dechlorination of PCDDs in mixed cultures and sediments (> 98% and 83%). These findings would promote the application of dechlorinating bacteria in targeted remediation and facilitate the respective studies on other POPs.

Efficient Organic Solar Cells Enabled by Chlorinated Nonplanar Small Molecules

Recently, the modification of end-capping groups for non-fullerene small molecules has been shown to be attractive as a promising structural-design strategy to construct effective electron acceptors for organic solar cells (OSCs) due to the tailorable molecular energy levels, tunable molar extinction coefficients, and easy-adjusting phase separation characteristic of the resultant acceptors. The application of chlorine substituents onto the ending groups of non-fullerene acceptors (NFAs) has positive effects such as an enhanced intermolecular charge-transfer effect between the electron-donating and electron-withdrawing structures, thus leading to broadening of the absorption regions. Lately, a series of NFAs containing appropriate nonplanar main chains have achieved promising performances. To further investigate the main-chain twisted NFAs, two chlorinated nonplanar small molecules were designed and prepared. Compared to the mono-chlorinated analogue (i-IEICO-2Cl), the dichlorinated molecule (i-IEICO-4Cl) had a bathochromic-shifted absorption spectrum with enhanced absorption intensity and a deeper molecular energy level. Blending with a medium band gap polymer donor (J52), the device of i-IEICO-4Cl shows more balanced charge mobilities and inhibitory charge recombinations, yielding a high efficiency of 12.16%, which is superior to 11.45% of an i-IEICO-2Cl-based OSC, revealing the effectiveness of chlorinated main-chain twisted acceptors for OSCs.

Solvent Effect on Assembling and Interactions in Solutions of Phenol: Infrared Spectroscopic and Density Functional Theory Study.

This work provides new insight into assembling of phenol in various solvents and competition between different kinds of interactions. To examine both weak and strong interactions, we selected a series of non-aromatic and aromatic solvents. Infrared spectra were measured at low (0.05 M) and high (2 M) phenol content. In addition, we performed density functional theory calculations of the structures and harmonic vibrational spectra of 1:1 complexes of phenol with the solvents and the associates of phenol from dimer to tetramer. Based on these results, we divided the solvents into three groups. The first group consists of non-aromatic solvents weakly interacting with phenol. Depending on the concentration, molecules of phenol in these solvents remain non-bonded or self-associated. In diluted solutions of phenol in chlorinated non-aromatic solvents do not appear free OH groups, since they are involved in a weak OH···Cl interaction. It is of note that in diluted solutions of phenol in tetramethyl ethylene both the non-bonded and bonded OH coexists due to solvent-solvent interactions. The second group consists of aromatic solvents with methyl or chlorine substituents. At low concentration, the molecules of phenol are involved in the phenol-solvent OH···π interaction and the strength of these interactions depends on the solvent properties. At a higher phenol content an equilibrium exists between phenol-solvent OH···π and phenol-phenol OH···OH interactions. Finally, the third group includes the aromatic and non-aromatic solvents with highly polar group (C≡N). In these solvents, regardless of the concentration all molecules of phenol are involved in the solute-solvent OH···NC interaction. Comparison of the experimental and theoretical band parameters reveals that molecules of phenol in non-aromatic solvents prefer the cyclic associates, while in the aromatic solvents they tend to form the linear associates.

Synthesis and Anti-Proliferation Activity Evaluation of Novel 2-Chloroquinazoline as Potential EGFR-TK Inhibitors.

A novel series of 2-chloroquinazoline derivatives had been synthesized and their anti-proliferation activities against the four EGFR high-expressing cells A549, NCI-H1975, AGS and HepG2 cell lines were evaluated. The preliminary SAR study of the scaffold of new compounds showed that the compounds with a chlorine substituent on R3 had a better anti-proliferation activity than those substituted by hydrogen atom or vinyl group. Among them, 2-chloro-N-[2-chloro-4-(3-chloro-4-fluoroanilino)quinazolin-6-yl]acetamide (10b) had the best activity, and the corresponding IC50 were 3.68, 10.06, 1.73 and 2.04 μM, respectively. And compound 10b had better or equivalent activity against four cell lines than Gefitinib. The activity of the compound 10b on the EGFR enzyme was subsequently tested. The Wound Healing of A549, AGS and HepG2 cells by this compound showed that the compound can inhibit the migration of cancer cells. Finally, the action channel of the compound 10b was supported by western blotting experiments. It provides useful information for the design of EGFR-TK inhibitors.

Influence of chlorine and methyl substituents and their position on the antimicrobial activities and crystal structures of 4-methyl-1,6-diphenylpyrimidine-2(1H)-selenone derivatives.

Derivatives of 4-methyl-1,6-diphenylpyrimidine-2(1H)-selenone show very strong antimicrobial activity. In order to extend the current knowledge about the features responsible for the biological activity, crystal structure analyses are presented for 4-methyl-1-(2-methylphenyl)-6-phenylpyrimidine-2(1H)-selenone (1), 4-methyl-1-(3-methylphenyl)-6-phenylpyrimidine-2(1H)-selenone (2), 4-methyl-1-(4-methylphenyl)-6-phenylpyrimidine-2(1H)-selenone (3) (all C18H16N2Se) and 1-(4-chlorophenyl)-4-methyl-6-phenylpyrimidine-2(1H)-selenone (4) (C17H13ClN2Se). Furthermore, the antibacterial and antifungal activities of these compounds were evaluated. All the presented derivatives crystallize in the space group P21/c with one molecule in the asymmetric unit. The molecular geometries differ slightly in the mutual orientation of the rings. The packing of molecules in the crystals is dominated by C-H...N and C-H...Se intermolecular interactions. Additionally, in the crystal structure of 4, C-H...Cl intermolecular interactions are observed. The introduction of a methyl or chlorine substituent improves the biological activity, while its position significantly affects biological activity only in case of the chlorine substituent.

Synthesis and Enzymological Characterization of Some 2-(Substitutedphenylamino) quinazolin-4(3H)-one Derivatives as Potent α-Glucosidase Inhibitors In Vitro

Background: α-Glucosidase is an important hydrolytic enzyme playing a vital role in digestion of carbohydrates. It catalyzes the final step of carbohydrates digestion in biological systems and converts unabsorbed oligosaccharides and disaccharides into monosaccharides, thus resulting in hyperglycemia for diabetic patients. In this respect, it has been considered as a therapeutic target for the treatment of type 2 diabetes since the enzyme inhibition delays carbohydrate digestion and monosaccharide absorption and subsequently reduces postprandial plasma glucose levels. Objective: In this study, fourteen 2-(substitutedphenylamino)quinazolin-4(3H)-one derivatives were synthesized and evaluated for their α-glucosidase inhibitory activities. Methods: The structures of the synthesized compounds were confirmed by spectral and elemental analyses. The biological activity and enzyme inhibition kinetic studies were performed by spectrophotometrical method using microplate reader. Physicochemical and drug-likeness properties of selected compounds were predicted by in silico method. Result: The biological activity results revealed that all of the synthesized compounds showed more potent α-glucosidase inhibitory activity in the range of IC50 = 58 ± 2 - 375 ± 15 μM when compared to the standard drug acarbose (IC50 = 892 ± 7 μM). Among the tested compounds, compound 12 bearing chlorine substituent at ortho position on N-phenyl ring displayed the highest inhibition with an IC50 value of 58 ± 2 μM against α-glucosidase. Furthermore, the enzyme inhibition kinetic study of the most active compound 12 indicated that the compound inhibited the α-glucosidase enzyme as uncompetitive with a Ki value of 63.46 μM. On the other hand, physicochemical and drug-likeness properties of selected compounds were predicted by in silico method. According to the results, it can be speculated that synthesized 2-phenylaminoquinazolin-4(3H)-one derivatives possessed favorable drug-likeness and pharmacokinetic profiles. Conclusion: In the light of results, 2-(substitutedphenylamino)quinazolin-4(3H)-one derivatives may serve as lead compounds to develop novel α-glucosidase inhibitors.

Enhancing the electrocatalytic activity of Fe phthalocyanines for the oxygen reduction reaction by the presence of axial ligands: Pyridine-functionalized single-walled carbon nanotubes

We have examined the electrocatalytic activity of iron phthalocyanine (FePc) and perchlorinated iron phthalocyanine 16(Cl)FePc for the oxygen reduction reaction (ORR) in alkaline medium with the two molecules either adsorbed on the external surface of single-wall carbon nanotubes (SWCNT) or covalently anchored via an axial pyridine ligand on pyridine-functionalized single-wall carbon nanotubes (py-SWCNT). Regardless of the particular phthalocyanine type, the ORR activity is higher when the substrate is py-SWCNT rather than SWCNT. The Tafel slopes for ORR are very similar for the two Fe macrocyclic complexes attached to SWCNTs in the two different configurations, suggesting a common rate-determining step for the ORR for all four catalysts. It is also observed that, for both the SWCNT and py-SWCNT supports, the ORR activity is higher for 16(Cl)FePc than for FePc. This is attributed to the electron-withdrawing effect of the peripheral and non-peripheral chlorine atoms in the macrocyclic ligand. While FeN4 macrocycles are known to be located on the strong binding side of a volcano correlation including several MN4 species, the chlorine substituents decrease the binding energy of O2 on the central Fe cation, thereby moving up the macrocycle catalyst towards the apex of the volcano correlation. Both the carbon surface and macrocyclic ligand effects were optimized with 16(Cl)FePc attached to py-SWCNT, which is more active than both FePc on SWCNT and FePc on py-SWCNT. Here we show that both the axial ligand and the electron withdrawing groups (-Cl) have a combined collaborative effect in increasing the catalytic activity for ORR of Fe-phthalocyanines confined on the external walls of single-wall carbon nanotubes.

Structure–Property Relationships of Precisely Chlorinated Thiophene‐Substituted Acceptors

AbstractSystematic investigation of three nonfullerene acceptors, BTIC‐4Cl‐T, BTIC‐4Cl‐TCl‐γ, and BTIC‐4Cl‐TCl‐b, with or without a chlorine substituent at the γ/b‐position of the side chain thiophene ring, reveals that molecular planarity, stacking structure, and photovoltaic performance of the compounds are dependent on the position of the chlorine substituent. Of the materials using thiophenes in conjugated side chains, BTIC‐4Cl‐T shows a relatively lower open‐circuit voltage of 0.81 V, decreased current density, leading to an efficiency of only 10.86%. BTIC‐4Cl‐TCl‐γ with chlorine at the γ‐position of the conjugated thiophene shows a 3D network structure, a greatly increased current density, and an efficiency of 14.35%. BTIC‐4Cl‐TCl‐b, with a chlorine atom in b‐position, is found to have been reformed to a quasi‐3D network, in which electron hopping can be efficiently realized in adjacently positioned, linearly arranged molecules due to S···S interactions. With this quasi‐3D network, BTIC‐4Cl‐TCl‐b promotes the open‐circuit voltage up to 0.86 V and has the highest efficiency (15.65%) among the three acceptors. These results prove that chlorination is an effective strategy to improve photovoltaic performance and highlights the decisive relationship between structural regulation and molecular arrangement. It also provides a good starting point for the exploration and design of next generation high‐performance materials.

Supramolecular Reorientation During Deposition Onto Metal Surfaces of Quasi-Two-Dimensional Langmuir Monolayers Composed of Bifunctional Amphiphilic, Twisted Perylenes.

Supramolecular dye structures, which are often ruled by π-π interactions between planar chromophores, crucially determine the optoelectronic properties of layers and interfaces. Here, we present the interfacial assembly of perylene monoanhydride and monoimide that do not feature a planar chromophore but contain chlorine substituents in the bay positions to yield twisted chromophores and hence modified π-stacking. The assembly of the twisted perylene monoanhydride and monoimide is driven by their amphiphilicity that ensures proper Langmuir layer formation. The shielding of the hydrophilic segment upon attaching an alkyl chain to the imide moiety yielded a more rigid Langmuir layer, even though the degrees of freedom were increased due to this modification. For the characterization of the Langmuir layer's supramolecular structure, the layers were deposited onto glass, silver, and gold substrates via Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) techniques and were investigated with atomic force microscopy and surface-enhanced resonance Raman spectroscopy (SERRS). From the similarity between all SERR spectra of the LS and LB layers, we concluded that the perylenes have changed their orientation upon LB deposition to bind to the silver surface of the SERRS substrate via sulfur atoms. In the Langmuir layer, the perylenes, which are π-stacked with half of the twisted chromophores, must already be inclined and cannot achieve full parallel alignment because of the twisting-induced steric hindrance. However, upon rotation, the energetically most favorable antiparallel aligned structures can be formed and bind to the SERRS substrate. Thus, we present, to the best of our knowledge, the first fabrication of quasi-two-dimensional films from twisted amphiphilic perylene monoimides and their reassembly during LB deposition. The relation between the molecular structure, supramolecular interfacial assembly, and its adoption during adsorption revealed here is crucial for the fabrication of defined functionalizations of metal surfaces, which is key to the development of organic (opto)electronic devices.

Unveiling the mechanistic roles of chlorine substituted phthalazinone-based compounds containing chlorophenyl moiety towards the differential inhibition of poly (ADP-ribose) polymerase-1 in the treatment of lung cancer

PARP-1 has become an attractive target in cancer treatment owing to its significant role in breast and ovarian cancers. The design of highly selective and effective poly (ADP ribose) polymerase-1 inhibitors has significant therapeutic advantages and has remained the core of several PARP-1-based drug discovery research. The pharmacophoric relevance of a chlorine substituent in a recent study led to the design of compounds 11c (meta-chlorophenyl) and 11d (para-chlorophenyl). In this study, we resolved the mechanistic effects of the changes in chlorine positional orientation, which underlie the inhibitory potencies and selectivity exhibited disparately by 11c and 11d. Compared to 11d, among other multiple higher-affinity complementary interactions with key site residues, the meta-Cl positioning in 11c facilitated its optimal motion and orientation towards conserved residues Arg878 and Asp766 with consistent pi-cation and pi-anion interactions, respectively, thereby favoring the stability of the ligand towards PARP-1. These could account for the higher inhibitory potency exhibited by 11c relative to 11d against PARP-1. The thermodynamics calculation revealed that 11c had a relatively higher total binding energy (ΔGbind) than 11d. We also observed that 11d displayed high deviations, compared to 11c, indicative of its unstable binding orientation. Furthermore, we reported in this study that the high involvement of electrostatic and van der Waal effects potentiated the binding affinity and strength of 11c (ΔEvdW = −50.58 and ΔEele = −27.20) relative to 11d (ΔEvdW = −49.46 and ΔEele = −19.96) at PARP-1 binding pocket. We believe the findings in this current study would provide valuable insights into the design of selective PARP-1 inhibitors containing chlorine substituent for cancer treatment, including lung cancer. Communicated by Ramaswamy H. Sarma

A Review on Synthesis, Structural, Flame Retardancy and Dielectric Properties of Hexasubstituted Cyclotriphosphazene.

Hexachlorocyclotriphosphazene is a ring compound consisting of an alternating phosphorus and nitrogen atom with two chlorine substituents attached to the phosphorus atom. The six chlorine atoms attached to this cyclo compound can be substituted with any different nucleophile that leads to changes in different chemical and physical properties. The major topics that were investigated in this research are the flame retardancy and dielectric properties of cyclotriphosphazene compounds. Cyclotriphosphazene compounds have high potential to act as a flame retardant, and this compound consists of two active elements attributed to its high flame-retardant character. This compound also demonstrated good ability as a flame retardant due to its low toxicity and less smoke produced. In addition, cyclotriphosphazene compounds were also investigated for their dielectric properties. Cyclotriphosphazene has high potential in the electrical field since it has dielectric properties that can be widely studied in the investigation of any potential application. This review presented literature studies focused on recent research development and studies in the field of cyclotriphosphazene that focused on synthesis, structural, flame retardancy, and dielectric properties of hexachlorocyclotriphosphazene compounds.

Impact of Chlorine Substitution on Electron Spin Relaxation of a Trityl Radical.

A perchlorotriarylmethyl tricarboxylic acid radical 99% enriched in 13C at the central carbon (13C1-PTMTC) was characterized in phosphate buffered saline solution (pH = 7.2) (PBS) at ambient temperature. Samples immobilized in 1:1 PBS:glycerol or in 9:1 trehalose:sucrose were studied as a function of temperature. Isotope enrichment at C1 creates a trityl that can be used to accurately measure microscopic viscosity. Understanding of the impact of the 13C hyperfine interaction on electron spin relaxation is important for application of this trityl in oximetry and distance measurements. The anisotropic 13C1 hyperfine couplings (Ax = Ay = 24 ± 2 MHz, Az = 200 ± 1 MHz) are larger than for the related 13C1-perdeuterated Finland trityl (13C1-dFT) and the g anisotropy (gx = 2.0013, gy = 2.0016, gz = 2.0042) is slightly larger than for 13C1-dFT. The tumbling correlation times (τR) for 13C1-PTMTC are 0.20 ± 0.02 ns in PBS and 0.40 ± 0.05 ns in 3:1 PBS:glycerol, which are shorter than for 13C1-dFT in the same solutions. T1 for 13C1-PTMTC is 3.5 ± 0.5 μs in PBS and 5.3 ± 0.4 μs in 3:1 PBS:glycerol, which are shorter than for 13C1-dFT due to faster tumbling, larger anisotropy of the 13C1 hyperfine, and about 30% larger contribution from the local mode. In immobilized samples T1 for 13C1-PTMTC is similar to that for 13C1-dFT and other trityls without chlorine or 13C1 substituents, indicating that the 13C1 and Cl substituents on the phenyl rings have little impact on T1. The temperature dependence of T1 was modeled with contributions from the direct, Raman, and local mode processes. Broadening of CW linewidths of about 0.6 G in fluid solution and about 2 G in rigid lattice is attributed to unresolved 35,37Cl hyperfine couplings.

Regio- and Stereoselective Synthesis of a New Series of Spirooxindole Pyrrolidine Grafted Thiochromene Scaffolds as Potential Anticancer Agents

A series of new spiro-heterocycles engrafted spirooxindole/pyrrolidine/thiochromene scaffolds was synthesized by the three-component 1,3-dipolar cycloaddition reactions in a fully controlled regio- and stereo-selective fashion. Condensation of several substituted isatin derivatives with L-proline generated the azomethine ylides which subsequently reacted with chalcones based thiochromene scaffold, and finally afforded the target spiro-compounds. This simple protocol furnished a structurally complex, biologically relevant spiro-heterocycles in good yields through a one-pot process. All synthesized chalcone-based thiochromene, along with the spirooxindole/pyrrolidine/thiochromene scaffolds, were tested for their anticancer activity against four cancer cell lines (PC3, HeLa, MCF-7, and MDA-MB231). Toxicity of these compounds was also evaluated against human fibroblast BJ cell line, and they appeared to be not cytotoxic. For the prostate cancer (PC3) cell line, the most active hybrid, among synthesized series, was compound (7f, IC50 = 8.7 ± 0.7 µM). The most potent spirooxindole/pyrrolidine/thiochromene hybrid against cervical (HeLa) cancer cells was compound (7k, IC50 = 8.4 ± 0.5 µM) having chlorine and p-trifluoromethyl substituents attached to phenyl rings. Finally, against the MCF-7 and MDA-MB231 breast cancer cell lines, compound (7d) was the most active member of this series (IC50 = 7.36 ± 0.37, and 9.44 ± 0.32 µM, respectively).

Recurring Real-Time Monitoring of Inflammations in Living Mice with a Chemiluminescent Probe for Hypochlorous Acid

Recurring Real-Time Monitoring of Inflammations in Living Mice with a Chemiluminescent Probe for Hypochlorous Acid

The effect of anthropogenic activities on the environmental fate of chlorinated paraffins in surface soil in an urbanized zone of northern China

Chlorinated paraffins (CPs) have been widely used as halogenated flame retardants and plasticizers since the mid-20th century. The prevalence of CPs in soil has been widely reported, but the distribution pattern of CPs in urbanized zones and their association with multiple socioeconomic variables have not been adequately explored. Herein, short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) were investigated in surface soil samples from Tianjin, China, a typical urbanized area. The concentration distributions of SCCPs and MCCPs showed similar trends in different administrative divisions and land use types: urban areas > suburbs > outer suburbs (p < 0.001) and residential areas > greenbelts > agricultural areas (p < 0.001). The CP congeners in residential surface soils mainly included those with longer carbon chains and high degree of chlorination, while the CP congeners in agricultural surface soils mainly consisted of those with shorter carbon chains and fewer chlorine substituents. Multiple statistical approaches were used to explore the association between socioeconomic factors and CP distribution. CP concentration was significantly correlated to population density and gross domestic product (GDP) (p < 0.001), and structural equation models incorporating administrative regional planning showed an indirect impact on the distribution of MCCP concentration due to the influence of regional planning on population density. These results highlight the association between CP contamination and the degree of urbanization, and this paper provides useful information toward mitigating the exposure risk of CPs for urban inhabitants.

Fluorination vs. Chlorination: Effect on the Sensor Response of Tetrasubstituted Zinc Phthalocyanine Films to Ammonia

In this work, the effect of fluorine and chlorine substituents in tetrasubstituted zinc phthalocyanines, introduced into the non-peripheral (ZnPcR4-np, R = F, Cl) and peripheral (ZnPcR4-p, R = F, Cl) positions of macrocycle, on their structure and chemiresistive sensor response to low concentration of ammonia is studied. The structure and morphology of the zinc phthalocyanines films (ZnPcR4) were investigated by X-ray diffraction and atomic force microscopy methods. To understand different effects of chlorine and fluorine substituents, the strength and nature of the bonding of ammonia and ZnPcHal4 molecules were studied by quantum chemical simulation. It was shown on the basis of comparative analysis that the sensor response to ammonia was found to increase in the order ZnPcCl4-np &lt; ZnPcF4-np &lt; ZnPcF4-p &lt; ZnPcCl4-p, which is in good agreement with the values of bonding energy between hydrogen atoms of NH3 and halogen substituents in the phthalocyanine rings. ZnPcCl4-p films demonstrate the maximal sensor response to ammonia with the calculated detection limit of 0.01 ppm; however, they are more sensitive to humidity than ZnPcF4-p films. It was shown that both ZnPcF4-p and ZnPcCl4-p and can be used for the selective detection of NH3 in the presence of carbon dioxide, dichloromethane, acetone, toluene, and ethanol.

Effect of the Chloro-Substitution on Electrochemical and Optical Properties of New Carbazole Dyes.

Carbazole derivatives are the structural key of many biologically active substances, including naturally occurring and synthetic ones. Three novel (E)-2-(2-(4-9H-carbazol-9-yl)benzylidene)hydrazinyl)triazole dyes were synthesized with different numbers of chlorine substituents attached at different locations. The presented research has shown the influence of the number and position of attachment of chlorine substituents on electrochemical, optical, nonlinear, and biological properties. The study also included the analysis of the use of the presented derivatives as potential fluorescent probes for in vivo and in vitro tests. Quantum-chemical calculations complement the conducted experiments.

Concise Chemoenzymatic Synthesis of Fasamycin A.

We report the development of a chemoenzymatic approach toward fasamycin A, a halogenated naphthacenoid that exhibits activities against methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus faecalis. The synthesis was accomplished in a convergent manner: two fragments were combined together in a Sammes annulation to afford a dimethylnaphthacenone system. Finally, an enzymatic halogenation was employed to introduce the requisite chlorine substituent of the natural product at a late stage.

Electrochemical Cleavage of Carbon‐Chlorine Bonds in Multiply Bridge‐Chlorinated Bicyclo[1.1.1]pentane‐1,3‐dicarboxylic Acids

AbstractReduction of five derivatives of bicyclo[1.1.1]pentane‐1,3‐dicarboxylic acid containing one to four chlorine substituents on methylene bridges were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. Electrochemical cleavage of C−Cl bonds and the reduction of H+ provided by dissociation of COOH groups are two competing processes characterized by different time constants. A concerted mechanism of C−Cl bonds cleavage is operative. The location of LUMO orbitals changes with increasing number of chlorine substituents from COOH sites to bicyclo[1.1.1]pentane. Carboxylic groups participate in the protonation of intermediates formed by the C−Cl bond rupture. The esterification of two derivatives eliminates the self‐protonation. Esters are reduced only at very negative potentials near the end of an available potential window.