Application of aza-BODIPY as a Nitroaromatic Sensor.

Nitroaromatic explosive detection with high sensitivity and selectivity is requisite for civilian and military safety and the ecosystem. In this study, aza boron dipyrromethene (aza-BODIPY) dye was selected as a fluorescent-based chemosensor against nitroaromatic compounds (NACs) including 2,4,6-trinitrophenol (picric acid, TNP), 2,4,6-trinitrotoluene (TNT), and 2,4-dinitrotoluene (DNT). This dye molecule exhibits sharp fluorescent behavior with high quantum yields beyond the near-infrared region (NIR) and is considered as a potential candidate for the detection of NACs. O'Shea's approach was used to synthesize tetraphenyl-conjugated aza-BODIPY molecules. Quenching of fluorescence emission of aza-BODIPY at 668 nm after the exposure to NACs was investigated under acetonitrile-water and acetonitrile-ethanol solvent conditions. The quenching responses and its mechanism were examined by considering the Stern-Volmer relationship Stern-Volmer constants (Ksv) for TNP (in water), TNP (in ethanol), TNT, and DNT, which are predicted to be 1420, 1215, 1364, and 968 M-1, respectively, all of which are sufficiently above the limit of detection (LOD) values. Thus, the present study opens up the possibility of the usage of aza-BODIPY molecules as a low-cost, light-weight sensor for the detection of NAC explosives.

Identification of a 3-(5-methyl-2-thiazolylamino)phthalide as a new minor groove agent.

A new 3-(5-methyl-2-thiazolylamino)phthalide molecule, 3-((5-methylthiazol-2-yl)amino)isobenzofuran-1(3H)-one, was synthesized and characterized experimentally by FT-IR, NMR, UV-Vis, and single-crystal X-ray analysis and theoretically by quantum chemical calculations. The single-crystal X-ray studies revealed that the compound crystallizes in the monoclinic space group P-21/c with unit-cell parameters a = 8.0550(6) Å, b = 6.1386(3) Å, c = 23.3228(18) Å, ß = 97.724(6)° and Z = 4. Optimized geometries and the vibrational frequencies were studied at the density functional theory (DFT) level by using the hybrid functional B3LYP with a 6-311 G (d,p) basis set. The title compound was evaluated for its anti-quorum sensing (anti-QS) activity on Chromobacterium violaceum 12472 and additionally for its antibacterial activity against Staphylococcus aureus 29213, Staphylococcus epidermidis 12228, Pseudomonas aeruginosa 27853, Escherichia coli 25922, and Proteus mirabilis 14153. The lowest MIC value was 0.24 µg/mL for S. aureus 29213 and the highest MIC value was 30.75 µg/mL for E. coli 25922. While anti-bacterial activity was observed in those other than the S. epidermidis and P. Mirabilis, anti-QS activity wasn't detected. Investigations on dsDNA binding affinity indicate that the title compound binds to dsDNA via the groove binding mode. Molecular docking calculations and molecular dynamics simulations results showed also that the title compound prefers binding to the minor groove of dsDNA and remains stable in the minor groove throughout the molecular dynamics simulation.Communicated by Ramaswamy H. Sarma.

An aza-Wittig/pi-furan cyclization approach toward the homoerythrina alkaloid (+/-)-selaginoidine.

[reaction: see text] A one-pot procedure was developed to efficiently prepare hexahydroindolinones containing a tethered furan ring. Reaction of a furanyl azide with Bu3P delivered the iminophosphorane, which was allowed to react with 1-methyl-(2-oxocyclohexyl)acetic acid to give the desired hexahydroindolinone ring system. Further treatment with trifluoroacetic acid afforded the tetracyclic lactam skeleton found in the alkaloid (+/-)-selaginoidine.

A study of vinyl radical cyclization using N-alkenyl-7-bromo-substituted hexahydroindolinones.

A new method for the synthesis of the octahydropyrrolo[3,2,1-ij]quinoline ring system that possesses the characteristic skeleton of the aspidosperma family of alkaloids has been developed. The method utilizes an intramolecular Diels-Alder reaction of an amido-substituted furan across a tethered indole pi-bond. To apply this strategy to the synthesis of the indole alkaloid spegazzinidine, it was necessary to address the problem of assembling the final D-ring of the pentacyclic skeleton. Radical cyclization of a model N-allyl-7-bromo-3a-methylhexahydroindolinone system was found to preferentially lead to the 6-endo-trig cyclization product, with the best yield being obtained under high dilution conditions. The six-membered cyclized product is generated through two reaction pathways: (a) 6-endo-trig ring closure and (b) rearrangement of an intermediate methylene-cyclopentyl radical obtained by 5-exo-trig cyclization. A number of related 7-bromo-substituted hexahydroindolinones containing tethered olefinic groups were prepared and found to undergo efficient cyclization under both radical and palladium-mediated reaction conditions. Vinyl radical cyclization with several N-butenyl-substituted systems afforded a mixture of 6-exo and 7-endo cyclization products. A protocol to introduce an ethyl substituent into the C20-position of the aspidospermidine skeleton was also developed.

Six- versus five-membered ring formation in radical cyclizations of 7-bromo-substituted hexahydroindolinones.

[reaction: see text] Radical cyclization of N-allyl-7-bromo-3a-methyl-hexahydroindol-2-one affords a six-membered ring product that prevails over the isomeric five-membered compound. The former product is generated through two reaction pathways: (a) 6-endo-trig ring closure and (b) rearrangement of an intermediate methylenecyclopentyl radical obtained by 5-exo-trig cyclization.