Reduced Phenalenyl in Catalytic Dehalogenative Deuteration and Hydrodehalogenation of Aryl Halides.

Dehalogenative deuteration reactions are generally performed through metal-mediated processes. This report demonstrates a mild protocol for hydrodehalogenation and dehalogenative deuteration of aryl/heteroaryl halides (39 examples) using a reduced odd alternant hydrocarbon phenalenyl under transition metal-free conditions and has been employed successfully for the incorporation of deuterium in various biologically active compounds. The combined approach of experimental and theoretical studies revealed a single electron transfer-based mechanism.

Accessing Heterobiaryls through Transition-Metal-Free C-H Functionalization.

Herein we report a transition-metal-free synthetic protocol for heterobiaryls, one of the most important pharmacophores in the modern drug industry, employing a new multidonor phenalenyl (PLY)-based ligand. The current procedure offers a wide substrate scope (24 examples) with a low catalyst loading resulting in an excellent product yield (up to 95%). The reaction mechanism involves a single electron transfer (SET) from a phenalenyl-based radical to generate a reactive heteroaryl radical. To establish the mechanism, we have isolated the catalytically active SET initiator, characterizing by a magnetic study.

Open-Shell Phenalenyl in Transition Metal-Free Catalytic C-H Functionalization.

Open-shell phenalenyl chemistry has widely been explored in the last five decades demonstrating its potential in various applications including molecular switch, spin memory device, molecular battery, cathode material, etc. In this article, we have explored another new direction of open-shell phenalenyl chemistry toward transition metal-free catalytic C-H functionalization process. A phenalenyl ligand, namely, 9-methylamino-phenalen-1-one (4a), promoted chelation-assisted single electron transfer (SET) process, which facilitates the C-H functionalization of unactivated arenes to form the biaryl products. The present methodology offers a diverse substrate scope, which can be operated without employing any dry or inert conditions and under truly transition metal based catalyst like loading yet avoiding any expensive or toxic transition metal. This not only is the first report on the application of phenalenyl chemistry in C-H functionalization process but also provides a low-catalyst loading organocatalytic system (up to 0.5 mol % catalyst loading) as compared to the existing ones (mostly 20-40 mol %), which has taken advantage of long known phenalenyl based radical stability through the presence of its low-lying nonbonding molecular orbital.

Copper-phenanthroline catalysts for regioselective synthesis of pyrrolo[3',4':3,4]pyrrolo[1,2-a]furoquinolines/phenanthrolines and of pyrrolo[1,2-a]phenanthrolines under mild conditions.

A new series of pyrrolo[3',4':3,4]pyrrolo[1,2-a]furoquinolines/phenanthrolines and pyrrolo[1,2-a]phenanthrolines were efficiently built up from an 8-hydroxyquinoline derivative or phenanthroline via 1,3-dipolar cycloaddition reaction involving non-stabilized azomethine ylides, generated in situ from the parent furo[3,2-h]quinoliniums/phenanthroliums, in presence of a copper(II) chloride-phenanthroline catalytic system. The methodology combines general applicability with high yields.

Different routes for the construction of biologically active diversely functionalized bicyclo[3.3.1]nonanes: an exploration of new perspectives for anticancer chemotherapeutics.

Cancer is the second most high-morbidity disease throughout the world. From ancient days, natural products have been known to possess several biological activities, and research on natural products is one of the most enticing areas where scientists are engrossed in the extraction of valuable compounds from various plants to isolate many life-saving medicines, along with their other applications. It has been noticed that the bicyclo[3.3.1]nonane moiety is predominant in most biologically active natural products owing to its exceptional characteristics compared to others. Many derivatives of bicyclo[3.3.1]nonane are attractive to researchers for use in asymmetric catalysis or as potent anticancer entities along with their successful applications as ion receptors, metallocycles, and molecular tweezers. Therefore, this review article discusses several miscellaneous synthetic routes for the construction of bicyclo[3.3.1]nonanes and their heteroanalogues in association with the delineation of their anticancer activities with few selective compounds.

Efficient synthesis of 3,3-diheteroaromatic oxindole analogues and their in vitro evaluation for spermicidal potential.

Syntheses of 3,3-diheteroaromatic oxindole derivatives has been achieved by coupling indole-2,3-dione (isatin) with differently substituted indoles and pyrrole in presence of I(2) in i-PrOH. The in vitro spermicidal potentials and the mode of spermicidal action of the synthesized analogues were evaluated and the derivative, 3,3-bis (5-methoxy-1H-indol-3-yl) indolin-2-one (3d) exhibited most significant activity.

Graphene oxide-phenalenyl composite: transition metal-free recyclable and catalytic C-H functionalization.

An efficient route towards a heterogeneous transition metal-free catalytic C-H functionalization using a covalently linked graphene oxide-phenalenyl conjugate is described herein (28 examples, which include a core of some biologically relevant biaryl and hetero-biaryls). It is an environmentally benign, economical and heterogeneous platform, whose catalytic activity can easily be regenerated through a simple washing-drying technique and the catalytic activity can be retained even after 10 cycles.

Ortho-C-H Benzylation of Aryl Imines with Benzyl Phosphates under Cobalt-Pyphos Catalysis.

Ortho-C-H benzylation of aryl ketimines with benzyl phosphates is achieved with the aid of a catalytic system consisting of a cobalt(II) salt, a phosphine/pyridine bidentate ligand, and a Grignard reagent under room-temperature conditions, affording a variety of diarylmethanes bearing o-acetyl or -acyl groups in moderate to good yields. Owing to the versatility of the o-acetyl group, the reaction opens useful synthetic routes to polycyclic compounds such as unsymmetrical anthracene, anthracenone, and anthraquinone derivatives.

Search for a potent microbicidal spermicide from the isolates of Shorea robusta resin.

BACKGROUND: An alarming increase in global population is the root cause of poverty, malnutrition, sexually transmitted infections (STIs) and many other social problems. Microbicidal spermicides possessing dual function of contraception and STI protection can effectively combat this problem, and their development is of utmost importance at present. STUDY DESIGN: A major metabolite isolated from Shorea robusta resin was spectroscopically characterized as asiatic acid. Spermicidal efficacy of the isolate was evaluated in vitro by a modified Sander-Cramer test. The mode of spermicidal action was assessed by (a) double fluoroprobe staining, (b) hypoosmotic swelling test and (c) scanning electron microscopy. Antimicrobial efficacy was assessed by disc diffusion and broth dilution methods using human isolates of bacteria (Escherichia coli ATCC 25938 and Pseudomonas aeruginosa 71) and fungus (Candida tropicalis). RESULTS: The minimum effective concentration of asiatic acid that induced instantaneous immobilization of rat spermatozoa in vitro was 125 mcg/mL. The mechanism of action involved disruption of sperm plasma membrane. The microbicidal efficacy was found to be moderate for vaginal pathogens, with no effect on normal vaginal flora. CONCLUSION: Asiatic acid possesses appreciable spermicidal and microbicidal potential and may be explored as an effective microbicidal spermicide.

Regio- and stereoselective synthesis of a library of bioactive dispiro-oxindolo/acenaphthoquino andrographolides via 1,3-dipolar cycloaddition reaction under microwave irradiation.

Dispiro-pyrrolidino/pyrrolizidino fused oxindoles/acenaphthoquinones have been derived from andrographolide via azomethine ylide cycloaddition to the conjugated double-bond under microwave (MW) irradiation. The reactions are chemo-, stereo-, and regioselective in nature. Change in amino acid from sarcosine/N-benzyl glycine to l-proline changes the regiochemistry. A representative library of 40 compounds along with in vitro anticancer evaluation is reported.

Amberlite-IRA-402 (OH) ion exchange resin mediated synthesis of indolizines, pyrrolo [1,2-a] quinolines and isoquinolines: antibacterial and antifungal evaluation of the products.

A number of indolizines and pyrrolo[1,2-a]quinolines/isoquinolines were prepared from phenacyl pyridinium, quinolinium and isoquinolinium salts derived from the reaction of the heterocycles with 2-bromo acetophenone with alkynes and alkenes using amberlite-IRA-402 (OH) ion exchange resin as the base. Antibacterial and antifungal studies were carried out against thirteen bacterial and four fungal strains, which revealed that three derivatives (4a, 4b, 7a) out of fifteen are effective against all the thirteen strains and one derivative, 10, showed dual antibactericidal and antifungal efficacy.

Electrochemically derived redox molecular architecture: a novel electrochemical interface for voltammetric sensing.

Redox-active molecular architectures are electrochemically derived on the electrode surface by Michael addition reaction of o-quinone with surface adsorbed nucleophiles. Electrogenerated o-quinone undergoes facile Michael addition reaction with nucleophile mercaptotriazole (MTz) and mercaptoimidazole (MIm) preassembled on Au electrode. The Michael addition reaction yields redox molecular architectures of 4-(3-mercapto-[1,2,4]triazol-1-yl)-benzene-1,2-diol (MTBD) and 4-(2-mercapto-imidazol-1-yl)-benzene-1,2-diol (MIBD). Solution pH controls the Michael addition reaction; the reaction of o-quinone with MTz nucleophile is more favorable in neutral pH whereas it is favorable in pH >or=9 with MIm. Michael addition of electrogenerated o-quinone with the nucleophile is quantitatively followed in real time using electrochemical quartz crystal microbalance (EQCM). The redox molecular architecture on the electrode surface is characterized by attenuated total reflection (ATR) spectral and electrochemical measurements. ATR spectral measurement confirms the Michael addition with the nucleophile. The redox molecular architecture displays reversible voltammetric response at 0.2 V corresponding to the redox reaction surface confined catechol moiety. The surface coverage of MTBD and MIBD on the electrode surface at pH 7.2 is estimated to be (5.4 +/- 0.2) x 10(-10) and (2.0 +/- 0.2) x 10(-10) mol/cm(2), respectively. Both redox molecular assemblies efficiently mediate the oxidation of reduced nicotinamide adenine dinucleotide (NADH) at a favorable potential. A large decrease in the overpotential associated with an enhancement in the voltammetric peak current with respect to the unmodified electrode is observed. Flow injection amperometric sensing of NADH is performed at the potential of 230 mV. These modified electrodes could detect NADH at micromolar level. Mixed molecular architecture of cysteamine (CYST) and MTz/MIm are developed for the interference free voltammetric sensing of NADH.