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Автор досліджує роль органів державної влади та місцевого самоврядування в процесі реалізації прав людини і громадянина на одержання інформації При цитуванні документа, використовуйте посилання http://essuir.sumdu.edu.ua/handle/123456789/36646Автор исследует роль органов государственной власти и местного самоуправления в процессе реализации прав человека и гражданина на получение информации При цитировании документа, используйте ссылку http://essuir.sumdu.edu.ua/handle/123456789/36646The author explores the role of state and local authorities in the implementation of human and civil rights to information When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3664

Neighboring Group Participation of 9-Anthracenylmethyl Group in Glycosylation: Preparation of Unusual <i>C</i>-Glycosides

A coupling of 2-O-arylmethylated d-glucose-derived thioglycosides with various alcohols in the presence of DMTST as an activator is described. The requisite glycosyl donors are efficiently prepared by one-pot procedures. When the aryl groups are phenyl, p-methoxyphenyl, 1-naphthyl, and 2-naphthyl groups, a mixture of α- and β-anomeric O-glycosides is obtained under the conditions, whereas when the aryl group is the 9-anthracenyl group, a highly stereoselective formation of the unusual C-glycosides in good yields via neighboring group participation of the 9-anthracenylmethyl group followed by coupling with a variety of alcohols is observed. Three new chiral centers including a quaternary carbon are created in one single step

Neighboring Group Participation of 9-Anthracenylmethyl Group in Glycosylation: Preparation of Unusual <i>C</i>-Glycosides

A coupling of 2-O-arylmethylated d-glucose-derived thioglycosides with various alcohols in the presence of DMTST as an activator is described. The requisite glycosyl donors are efficiently prepared by one-pot procedures. When the aryl groups are phenyl, p-methoxyphenyl, 1-naphthyl, and 2-naphthyl groups, a mixture of α- and β-anomeric O-glycosides is obtained under the conditions, whereas when the aryl group is the 9-anthracenyl group, a highly stereoselective formation of the unusual C-glycosides in good yields via neighboring group participation of the 9-anthracenylmethyl group followed by coupling with a variety of alcohols is observed. Three new chiral centers including a quaternary carbon are created in one single step

Dicopper Complexes with Anthyridine-Based Ligands: Coordination and Catalytic Activity

Two new anthyridine-based ligands, 5-phenyl-2,8-bis­(2-pyridinyl)-1,9,10-anthyridine (<b>L</b>_<b>3</b>) and 5-phenyl-2,8-bis­(6′-bipyridinyl)-1,9,10-anthyridine (<b>L</b>_<b>4</b>), were designed for accommodation of dimetallic systems with the metal ions separated by ∼5 Å. Complexation of Cu­(ClO₄)₂ with <b>L</b>_<b>3</b> and <b>L</b>_<b>4</b> provided the corresponding dicopper complexes [{Cu₂(<b>L</b>_<b>3</b>)­(H₂O)₄­(CH₃CN)₂}­(ClO₄)₄] (<b>3</b>) and [{Cu₂(<b>L</b>_<b>4</b>)­(μ-ClO₄)₂}­(PF₆)₂] (<b>4</b>), respectively. Both complexes were characterized by spectroscopic methods, and the detail structural features were further confirmed by X-ray crystallography. Structural analyses of <b>3</b> and <b>4</b> reveal the Cu···Cu distances in the complexes being 4.9612(7) and 5.013 (2) Å, respectively. Both complexes are active in the catalytic oxidation of benzyl alcohols into the corresponding aldehydes. Furthermore, complex <b>4</b> appears to be a good catalyst for the oxidative coupling of primary alcohols into the corresponding esters with the use of hydrogen peroxide as the oxidant in an aqueous medium. The possible cooperative interactions between the metal ions during the catalysis are discussed

An Anthyridine-Based Pentanitrogen Donor Switches from Mono- to Tetradentate with Pd(II) Ions

Treatment of 5-phenyl-2,8-bis­(2-pyridinyl)­anthyridine (L) with (PPh3)2PdCl2 or (dppe)­PdCl2 in the presence of a silver salt resulted in the formation of [trans-(PPh3)2PdLCl]­(BF4) (1a), [trans-(PPh3)2PdL(MeCN)]­(BF4)2 (1b), [trans-(PPh3)2PdLCl]­(PF6) (1c) ,or [cis-(dppe)­PdLCl]­(BF4) (4), respectively. The ligand L in these complexes acts as a monodentate ligand with N(10) of anthyridine binding to the metal center. In the presence of PPh3, dinuclear complexes [Pd2L(CH3CN)2Cl2]­(BF4)2 (2) and [Pd2L(CH3CN)4]­(BF4)4 (3) readily underwent dechelation to yield 1a,b, respectively, whereas the reaction of 2 with dppe gave 4. On the other hand, treatment of 1a and 4 with S8 in the presence of a sufficient amount of palladium ions provided the corresponding dinuclear complex 2. Furthermore, this kind of substitution is also applicable with the Pd-Me complex [Pd2L(CH3CN)2Me2]­(BF4)2 (5), which could be prepared from complexation of L with 2 equiv of [(COD)­Pd­(CH3CN)­Me]­(BF4). Thus, [trans-(PPh3)2PdLMe]­(BF4) (7) was obtained by the reaction of 5 with PPh3. However, the reaction of PPh3 with [Pd2L(CH3CN)2(MeCO)2]­(BF4)2 (6), a CO insertion product of 5, gave a messy result. The catalytic activity of these complexes in the Suzuki–Miyaura coupling of aryl halide with arylboronic acid under a CO atmosphere was investigated. Crystal structures of 1c, 4, 5, and 7 are reported to confirm their structural details. This work demonstrates the novelty of L as a hypodentate ligand toward palladium ions

Palladium-Catalyzed Vinylation of Cyclopentenes with Inverted <i>Z,E</i>-Isomerism of Vinylic Substrates

A palladium-promoted Mizoroki–Heck type reaction employing a directing-group strategy to efficiently produce the coupled vinyl cyclopentenes with excellent regio- and stereoselectivity is reported. Typically, a Pd-catalyzed reaction of 2-(cyclopent-2-en-1-yl)-N-tosylacetamide (1a) with (E)-styryl bromides gave cis-2-((Z)-styryl)­cyclopent-3-en-1-yl-N-tosylacetamide (3e), an allylic substitution product. Interestingly, we have found that the E,Z-stereochemistry of vinylic substrates is inverted in those products. The mechanism of this catalytic reaction is discussed

Palladium(II) Complexes Containing P∼N∼O Donors. Ligand Effect of Tridentate versus Bidentate Coordination on the Oligomerization of Ethylene

Palladium complexes containing the [(RO)nC6H5-nC]N(C6H4PPh2-o) (P∼N∼O) ligand were synthesized, and the hemilability of the coordinating oxygen donors toward the metal center was studied. In the case of oxygen being a ether functionality (R = Me), acetonitrile readily replaces the tridentate ether donor in [Pd(P∼N∼O)Me]BF4 (1) to yield [Pd(P∼N∼O)(MeCN)Me]BF4 (2). The labile nature of the ether donor assists the complex 1 in catalyzing the oligomerization of ethylene. Presumably, the temporary coordination of the ether donor to the vacant site during migratory insertion suppresses the β-elimination, which allows the elongation of the alkyl chain

Pentaleno[1,2‑<i>c</i>]pyrroles: Tricyclic 5/5/5 Fused Rings

A novel method for the preparation of tetrahydropentaleno[1,2-c]pyrroles (8) is described via the reaction of anilines with 1-en-4-yn-3-ols in the presence of Lewis acid. Oxidation of 8 with Br2 gave pentaleno[1,2-c]pyrroles (10), which is the first reported tricyclic 5/5/5 ring with a fully conjugated system. Structures of these obtained compounds were characterized by spectroscopic methods, and compounds 8a,b and 10c were further confirmed by X-ray crystallographic determination

New Bulky Phosphino−Pyridine Ligands. Palladium and Nickel Complexes for the Catalytic Polymerization and Oligomerization of Ethylene

Two bulky phosphino−pyridine ligands (6-mesityl-2-((diarylphosphino)methyl)pyridine, P∼N) were successfully prepared by means of Suzuki coupling of mesitylboronic acid with 6-bromo-2-picoline followed by phosphinylation. These ligands readily form the palladium and nickel complexes upon treatment with (COD)PdMeCl and (DME)NiBr2, respectively. These P∼N chelating Pd(II) and Ni(II) complexes were characterized by both spectral data and X-ray crystallography. The coordination geometry around the metal center is square planar for the Pd(II) complexes and tetrahedral for the Ni(II) complexes. The cationic methylpalladium(II) complexes showed poor activity in the catalytic polymerization of ethylene, but the nickel complexes were highly active with the activation of MAO. The nickel complexes catalyzed the polymerization of ethylene with an Al/Ni ratio of 150, whereas di- and trimerization was observed when the Al/Ni ratio is 500. The obtained polyethylenes are highly crystalline

Pd-Promoted Cyclization of (<i>Z</i>)‑Pent-2-en-4-yn-1-yl Alkanoates Leading to Furans via an Acyl Group Shift and Further Synthetic Transformation

Palladium-promoted acyl migration was observed in the reaction of (Z)-pent-2-en-4-yn-1-yl alkanoates in the presence of DBU to yield 2-(alkanoylmethyl)furan derivatives (2) in high yields. Compounds 2 then underwent oxidative decarbonylation to afford 2-acylfurans with O2 as the oxidant under mild and metal-free conditions. The mechanistic pathway of the reaction involving an intramolecular cyclization and acyl group shift is discussed