F 76 Formation of polynuclear palladium complexes with the benzimidazole-2-thiolate anion [Electronic resource] / M. O. Talismanova, A. A. Sidorov, G. G. Aleksandrov, V. N. Charushin, S. K. Kotovskaya, I. L. Eremenko, I. I. Moiseeva // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 2008. - Vol. 57, № 1. - P47-55 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: The reactions of palladium(II) salts with 2-mercaptobenzimidazole (HL) and its 5,6-difluorinated derivative (HLF) were investigated. In the presence of hydrochloric acid, PdCl2 and K2PdCl4 react with HL and HLF in the ethanol—water and acetonitrile—water systems to form the mono-nuclear dicationic complexes [Pd(HL)4]Cl2 (1) and [Pd(LF)4]Cl2 (2). In the absence of HCl, the reactions afford the tetranuclear complex Pd4[(L)2(3-S,N-(L))2(S,N-(L))4] (3). The reaction of triethylamine with an ethanolic solution of 3 leads to degradation of 3 and the formation of the lantern-type dinuclear complex Pd2[2-(L)4] (4), in which the palladium atoms are in the nonequivalent coordination environment, PdN4 and PdS4. The reaction of K2PdCl4 with HL or HLF in the THF—water or acetonitrile—water systems (for the reaction with HLF) in the presence of Et3N produces the lantern-type dinuclear complexes Pd2[(?S,N-(L3))4] and Pd2[(S,N)(LF))4] (5), in which the metal atoms are in the equivalent coordination environment (cis-PdN2S2) \\\\Expert2\\nbo\\Russian Chemical Bulletin\\2008, 57 (1), 47.pdf |
P 17 Palladium(II)-Catalyzed Oxidative C–H/C–H Coupling and Eliminative SNH Reactions in Direct Functionalization of Imidazole Oxides with Indoles / M. V. Varaksin, I. A. Utepova, O. N. Chupakhin, V. N. Charushin // Journal of Organic Chemistry. - 2012. - Vol.77, №20. - С. 9087-9093 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): IMIDAZOLE OXIDES -- INDOLES Аннотация: Two novel synthetic approaches to realize the direct C(sp2)–H bond functionalization in cyclic nitrones are reported. Palladium(II)-catalyzed oxidative C–C coupling of 2,2-dialkyl-4-phenyl-2H-imidazole 1-oxides with indoles was shown to result in the formation of 5-indolyl-3-yl derivatives, while nucleophilic substitution of hydrogen (SNH) at C(5) of the same imidazole system was found to afford the corresponding deoxygenated compounds \\\\Expert2\\nbo\\Journal of Organic Chemistry\\2010, v.77, p.9087.pdf |
M 65 Microwave-assisted palladium-catalyzed C–C coupling versus nucleophilic aromatic substitution of hydrogen (SNH) in 5-bromopyrimidine by action of bithiophene and its analogues [Электронный ресурс] / E. V. Verbitskiy, E. M. Cheprakova, E. F. Zhilina, M. I. Kodess, M. A. Ezhikova, M. G. Pervova, P. A. Slepukhin, V. N. Charushin // Tetrahedron. - 2013. - Vol.69, №25. - P5164-5172 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): C–H BOND ACTIVATIONS -- PYRIMIDINES -- PALLADIUM Аннотация: 5-Bromopyrimidine reacts with 2,2′-bithiophene, [2,2′:5′,2″]terthiophene and 2-phenylthiophene in the presence of a palladium catalyst to give 5-(het)aryl substituted pyrimidines due to the palladium-catalyzed aryl–aryl C–C coupling. However 5-bromo-4-(het)aryl-pyrimidines have been prepared from the same starting materials through the SNH-reaction catalyzed by a Lewis acid. Conditions for both types of reactions were optimized. All components of the reaction mixtures, including by-products, have been elucidated by gas–liquid chromatography/mass-spectrometry. Evidence for the structure of 4- and 5-bithiophenyl-substituted pyrimidines has first been obtained by means of X-ray crystallography analysis. Molecular orbital calculations (TDDFT), as well as the redox and optical measurements for all new compounds have also been performed \\\\Expert2\\NBO\\Tetrahedron\\2013, v. 68, p. 5164.pdf |
D 62 Direct C(sp2)-H Bond Functionalization in Cyclic Aldonitrones: Palladium(II)-Catalyzed Oxidative Cross-Coupling and Eliminative SNH Reactions / M. V. Varaksin, O. N. Chupakhin, V. N. Charushin, S. V. Mikhaylov, I. A. Utepova, B. A. Trofimov // 18th European Symposium on Organic Chemistry ESOC-2013, Marseille, France, 7-12 July 2013 : book of abstracts. - Marseille, France, 2013. - С. 329 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): PALLADIUM(II) -- SNH REACTIONS -- CYCLIC ALDONITRONES |
T 98 Two Approaches in the Synthesis of Planar Chiral Azinylferrocenes [Electronic resource] / I. A. Utepova, O. N. Chupakhin, P. O. Serebrennikova, A. A Musikhina, V. N. Charushin // Journal of Organic Chemistry. - 2014. - Vol. 79, № 18. - С. 8659-8667. - Bibliogr. : p. 8666-8667 (34 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): CHIRAL AZINYLFERROCENES -- CROSS-COUPLING REACTION -- HALOGENATED AZINES Аннотация: Two synthetic routes to the chiral azinylferrocenes (CAFs) 5 and 15, key intermediates for the synthesis of new enantiomerically enriched P,N-ligands, have been compared. The first approach is based on the palladium-catalyzed cross-coupling reaction of halogenated azines with organozinc derivatives of ferrocenes (the Negishi reaction). The second approach exploits a new synthetic methodology, which provides a shorter pathway, through the direct C–H functionalization of aromatics by the C–C coupling of halogen-free (hetero)arenes with lithium ferrocenes bearing stereogenic C and S atoms. The palladium complexes of P,N-ligands have been used as catalysts for the Tsuji–Trost reaction, which proceeds with high enantioselectivity to give allylic substitution products in good yields. \\\\expert2\\nbo\\Journal of Organic Chemistry\\2014, v.79, p.8659.pdf |
S 98 Synthesis of 6-thienyl-substituted 2-amino-3-cyanopyridines [Electronic resource] / E. V. Verbitskiy, E. M. Cheprakova, M. G. Pervova, G. G. Danagulyan, G. L. Rusinov, O. N. Chupakhin, V. N. Charushin // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 2015. - С. 689-694. - Bibliogr. : p. 694 (25 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): PYRIMIDINES -- TRANSFORMATIONS OF HETEROCYCLE -- PYRIDINES Аннотация: An efficient method for the synthesis of 6-thienyl-substituted 2-amino-3-cyanopyridines by the ring transformation in the corresponding pyrimidines was developed. Further modification of the pyridines obtained under conditions of a room temperature aerobic Suzuki reaction in the presence of trans-bis(dicyclohexylamine) palladium(II) acetate as a catalyst was studied. \\\\expert2\\nbo\\Russian Chemical Bulletin\\2015, 64 (3), 689-694.pdf |
S 98 Synthesis and Photophysical Studies of 2-(Thiophen-2-yl)-4-(morpholin-4-yl) quinazoline Derivatives [Electronic resource] / E. V. Nosova, T. N. Moshkina, G. N. Lipunova, D. S. Kopchuk, P. A. Slepukhin, I. V. Baklanova , V. N. Charushin // European Journal of Organic Chemistry. - 2016. - № 16. - С. 2876-2881 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): PHOTOPHYSICS -- CHARGE TRANSFE -- FLUORESCENCE Аннотация: The synthesis of a series of push-pull aryl and arylethynyl 2-(thiophen-2-yl) quinazoline derivatives is presented. The photophysical properties of the newly generated compounds are also described. Functionalization of the (2-thienyl) quinazoline fluorophore at the 5'-position with aryl and arylethynyl moieties was performed using bromination and subsequent palladium-catalyzed cross-coupling reactions. Optical studies revealed that 4-(diethylamino) phenyl and 4-(diphen-ylamino) phenyl derivatives emit green light upon irradiation, whereas their 4-(9H-carbazol-9-yl) phenyl, methoxyphenyl, thienyl and arylethynyl counterparts are characterized by blue light emission capabilities. The effect of protonation has also been studied, and the ability of some of these molecules to function as colorimetric and luminescent pH sensors has been demonstrated with significant color changes and luminescence switching upon the introduction of acid. \\\\expert2\\NBO\\European Journal of Organic Chemistry\\2016, №16. p.2876-2881.pdf |
A 10 A new synthetic approach to fused nine-ring systems of the indolo[3,2-b] carbazole family through double Pd-catalyzed intramolecular C-H arylation [Electronic resource] / R. A. Irgashev, N. A. Kazin, G. A. Kim, G. L. Rusinov, V. N. Charushin // RSC Advances. - 2016. - Vol. 6, № 74. - С. 70106-70116 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): IGHT-EMITTING-DIODES -- BIPOLAR HOST MATERIALS -- HOLE-TRANSPORTING MATERIALS Аннотация: A series of new polycyclic compounds bearing the 5,11-dihydroindolo[3,2-b] carbazole ring system, as the common motif of their nine-ring scaffolds, has been successfully prepared with the usage of an efficient two-step strategy, based on the double Friedel-Crafts acylation of 5,11-dihexyl-6,12-di(hetero) aryl-substituted 5,11-dihydroindolo[3,2-b] carbazoles with 2-iodobenzoyl chloride in the presence of SnCl4, followed by regioselective palladium-catalyzed cyclization of the obtained 2,8-bis(2-iodobenzoyl) derivatives into the desired fused 9H-fluoren-9-ones. Some modifications of these nine-ring structures have been performed to afford compounds of the same family bearing the 9H-fluorene fragments. Basic photophysical and electrochemical properties as well as thermal stability of the new fused indolo[3,2-b] carbazole derivatives have been determined. \\\\expert2\\NBO\\RSC Advances\\2016. Vol. 6, N 74. P. 70106.pdf |
A 10 A new route towards dithienoquinazoline and benzo[f]thieno[3,2-h]quinazoline systems using Pd-catalyzed intramolecular cyclization under microwave irradiation [Electronic resource] / E. V. Verbitskiy, G. L. Rusinov, O. N. Chupakhin, V. N. Charushin // ARKIVOC. - 2016. - № 4. - С. 204-216 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): PYRIMIDINES -- INTRAMOLECULAR CYCLIZATIONS -- FUSED RING SYSTEMS -- THIENOACENES Аннотация: A novel synthetic route to novel thienoacene systems bearing a fused pyrimidine ring is proposed. The commercially available 5-bromopyrimidine is used as the starting material to obtain various dithienoquinazoline and benzo[f]thieno[3,2-h] quinazoline systems through the Suzuki cross-coupling, nucleophilic aromatic substitution of hydrogen (the S-N(H) reaction), and finally palladium-catalyzed intramolecular cyclization under microwave irradiation. Redox properties of some of the new compounds have been investigated. The data obtained show that these systems have plausible potential for use in organic electronic applications. \\\\expert2\\NBO\\ARKIVOC\\2016, p.204-216.pdf |
Oxidative C–H functionalization of arenes: main tool of 21st century green chemistry. A review / A. V. Shchepochkin, F. V. Antipin, V. N. Charushin, O. N. Chupakhin // Doklady Chemistry. - 2021. - Vol. 499, № 1. - P123-157 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Recent advances in the field of direct oxidative C–H functionalization of inactivated arenes, as one of the main tools of green chemistry, are discussed. Examples of building carbon–carbon, carbon–oxygen, carbon–nitrogen, and carbon–sulfur bonds, using catalysis with palladium compounds, oxidation with hypervalent iodine derivatives, and through electrochemical and photochemical transformations, are given. |
Synthesis of heteroannulated indolopyrazines through domino N-H palladium-catalyzed/metal-free oxidative C-H bond activation / Y. A. Kvashnin, E. V. Verbitskiy, E. F. Zhilina [et al.] // ACS Omega. - 2020. - Vol. 5, № 25. - P15681-15690 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: A convenient approach to [1,2,5]oxadiazolo[3′,4′:5,6]pyrazino[2,3-b]indoles and their heteroannulated analogues bearing various aryl substituents in the backbone has been developed. This synthetic protocol is based on Pd-catalyzed Buchwald–Hartwig and subsequent annulation by intramolecular oxidative cyclodehydrogenation. The photophysical properties for new polycycles have been measured. |