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Highly stereoselective formation of 1,3-dioxolanes by photocatalytic ring opening reacrions of alpha-epoxyketones in acetone solution using 1-benzyl-2,4,6-triphenylpyridinium tetrafluoroborate (NBTPT)

Highly stereoselective formation of 1,3-dioxolanes has been observed on photoinduced electron transfer ring opening of alpha-epoxyketones by 1-benzyl-2,4,6-triphenylpyridinium tetrafluoroborate (NBTPT) in acetone solution. The presence of various substituents on the donor molecule has not affected the rate of the ring opening and also stereoselectivity of the reaction too much. Stepwise addition of the photocatalyst leads to decreasing of irradiation time and increasing of the yield of products. Photoinduced electron transfer deoxygenation and isomerization of some alpha-epoxyketones has also been observed. Cyclic voltammetric study of the photocatalyst shows a greater tendency of NBTPT for accepting an electron in the excited state.{A figure is presented}.

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Catalyst-free Decarboxylation and Decarboxylative Giese Additions of Alkyl Carboxylates through Photoactivation of Electron Donor-Acceptor Complex

We report herein a catalyst-free method to perform decarboxylative conjugated addition and hydrodecarboxylation of aliphatic N-(acyloxy)phthalimides (redox active esters, RAEs) through photoactivation of electron-donor-acceptor (EDA) complex with Hantzsch ester (HE) in N,N-dimethylacetamide (DMA) solution. The reactions present a green method to decarboxylatively construct carbon-carbon bond and to perform hydrodecarboxylation with broad substrate scope and functional group tolerance under mild blue light irradiation condition without recourse of popularly used photoredox catalysts. (Figure presented.).

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A new dual probe for hydrogen abstraction

A new dual (fluorescent and spin) probe is described, where a N-aryl-2,4,6-triphenylpyridinium fluorophore is attached to a TEMPO fragment through an amide link. The resulting sensor 4 was evaluated as a hydrogen-abstracting agent in acetonitrile and in an aqueous solution of reduced Triton-X 100, being as resistant to hydrolysis as quinoline-TEMPO 1, but more hydrophobic than this probe.

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Metal catalyst and ligand design,
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Reactive Oxygen Species (ROS)-vs Peroxyl-Mediated Photosensitized Oxidation of Triphenylphosphine: A Comparative Study

The oxidation of triphenylphosphine in the presence of various photocatalytic systems (dicyanoanthracene/biphenyl, N-methylquinolinium, triphenylpyrylium, and thiatriphenylpyrylium tetrafluoroborate) was investigated by means of both steady state and laser flash photolysis experiments. The effect of different additives (including 1,4-benzoquinone, diphenylsulfoxide, tetramethylethylene, and sodium azide) on the photosensitized oxidation was investigated in order to fully characterize the involved intermediates. Photoinduced electron transfer and final regeneration of the catalyst occur when dicyanoanthracene and N-methylquinolinium are used, while in cage oxygen transfer to the photoexcited (thio)pyrylium derivatives have been characterized in the last two cases.

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Nucleophilic Displacements of N-Aryl and Heteroaryl Groups. Part 4. Pyrylium-mediated Transformations of Heteroarylamines into Pyridinium Salts and their Inter- and Intra-molecular Displacement

Heteroarylamines and the appropriate pyrylium salts give 1-heteroaryl-2-ethoxycarbonyl-4,6-diphenylpyridinium, and 1-(2-pyridyl)-2,6-diethoxycarbonyl-4-phenylpyridinium salts.Hydrolysis and decarboxylation afford 1-(2-pyridyl)-2,4-diphenyl- and 1-(2-pyridyl)-4-phenyl-pyridinium salts.Neither these, nor their 2,4,6-triphenyl analogues underwent smooth nucleophilic substitution. 1-Pyrimidin-2-yl- and 1-(4,6-dimethylpyrimidin-2-yl)-2-ethoxycarbonyl-4,6-diphenylpyridinium with ethanolic NaOEt smoothly formed the corresponding pyrimidin-2-ones via intramolecular attack.

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Fluorescence Properties of Pyrylium and Thiopyrylium Salts

Due to their very substantial fluorescence emission, pyrylium and thiopyrylium salts are widely used and laser dyes and photosensitizers.This paper deals with the fluorescence properties (quantum yields and wavelengths of the fluorescence maxima as well as the lifetimes of the singlet excited states) of eight pyrylium and ten thiopyrylium salts, with special emphasis on the effect of alpha and gamma substitutions of the heterocycle.

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Bridged pyridoquinazoline or phenanthroline compounds and organic semiconducting material comprising that compound

The present invention relates to a compound according to formula: an organic semiconducting material comprising that compound and organic electroluminescent device.

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Role of sulfide radical cations in electron transfer promoted molecular oxygenations at sulfur

The methylene blue, N-methylquinolinium tetrafluoroborate, and pyrylium-cation-sensitized photooxygenations of 5H, 7H-dibenzo[b,g] [1,5]dithiocin, 1, and 1,5-dithiacyclooctane, 2, have been investigated. The methylene blue sensitized reactions exhibit all of the characteristics of a singlet oxygen reaction including isotope effects for the formation of a hydroperoxysulfonium ylide and the ability of 1 and 2 to quench the time-resolved emission of singlet oxygen at 1270 nm. The product compositions in the N-methylquinolinium tetrafluoroborate and pyrylium-cation-sensitized reactions are dramatically different and are both different from that anticipated for the participation of singlet oxygen. This argues for different reaction mechanisms for all three sensitizers. However, both the quinolinium and pyrylium-cation-sensitized reactions display all of the characteristics of electron-transfer-initiated photooxygenations. Both sensitizers were quenched at nearly diffusion-limited rates by 1 and 2. Laser flash photolysis of mixtures of either sensitizer and 1 or 2 resulted in direct observation of the reduced sensitizer and the sulfide radical cation. In addition, electron-transfer reactions involving both sensitizers were shown to be exergonic. These results are consistent with the previously proposed outer sphere electron-transfer mechanism for N-methylquinolinium tetrafluoroborate and were used to argue for a new inner sphere mechanism for the pyrylium cation reactions.

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Reductive (3 + 2) Annulation of Benzils with Pyrylium Salts: Stereoselective Access to Furyl Analogues of cis-Chalcones

An unprecedented reductive (3 + 2) annulation of both symmetrical and unsymmetrical benzils with pyrylium salts mediated by P(NMe2)3 is described, leading to facile and stereoselective access to the challenging cis-chalcones decorated by various substituted furyl rings under mild conditions. Rather than the extensively studied C1 synthons, the Kukhtin-Ramirez adducts derived from benzils serve as the underexplored C3 synthons in this (3 + 2) annulation with the 2,3-double bond of the 2,6-disubstituted pyrylium ions.

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Metal catalyst and ligand design,
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PYRAZOLO(1,5-c)PYRIMIDINES FROM PYRYLIUM SALTS AND AMIDRAZONES AND PYRIDINE IMIDOYL-N-IMIDES FROM IMIDOYL CHLORIDES

2,4,6-Triphenylpyrylium salts react with unsubstituted amidrazones to give dihydropyrazolo(1,5-c)pyrimidines or salts of pyridine imidoyl-N-imides.Pyridine imidoyl-N-imides are conveniently prepared from N-aminopyridinium and imidoyl chlorides.

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Metal catalyst and ligand design,
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