TY - JOUR AU - Molnár, Márk AU - Gáti, Tamás AU - Bényei, Attila Csaba AU - Nyerges, Miklós TI - Synthesis of spiro[piperidine-4,3′-pyrrolo[3,4-c]quinolines via 1,3-dipolar cycloaddition of azomethine ylides and 3-Nitro-2(1H)-quinolones JF - TETRAHEDRON LETTERS J2 - TETRAHEDRON LETT VL - 139 PY - 2024 PG - 6 SN - 0040-4039 DO - 10.1016/j.tetlet.2024.155001 UR - https://m2.mtmt.hu/api/publication/34749525 ID - 34749525 LA - English DB - MTMT ER - TY - JOUR AU - Farkas, Vajk AU - Csókás, Dániel AU - Erdélyi, Ádám AU - Turczel, Gábor AU - Bényei, Attila Csaba AU - Nagy, Tibor AU - Kéki, Sándor AU - Pápai, Imre AU - Tuba, Róbert TI - “Inverted” Cyclic(Alkyl)(Amino)Carbene (CAAC) Ruthenium Complex Catalyzed Isomerization Metathesis (ISOMET) of Long Chain Olefins to Propylene at Low Ethylene Pressure JF - ADVANCED SCIENCE J2 - ADV SCI VL - 11 PY - 2024 IS - 12 SN - 2198-3844 DO - 10.1002/advs.202400118 UR - https://m2.mtmt.hu/api/publication/34742565 ID - 34742565 N1 - Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Magyar tudósok körútja 2, Budapest, H-1117, Hungary Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, Szent Gellért tér 4, Budapest, H-1111, Hungary Institute of Organic Chemistry, Research Centre for Natural Sciences, Magyar tudósok körútja 2, Budapest, H-1117, Hungary Research Centre for Biochemical, Environmental and Chemical Engineering, Department of MOL Hydrocarbon and Coal Processing, University of Pannonia, Egyetem u. 10, Veszprém, H-8210, Hungary Department of Physical Chemistry, Faculty of Science and Technology, University of Debrecen, Egyetem tér 1, Debrecen, H-4032, Hungary Department of Applied Chemistry, Faculty of Science and Technology, University of Debrecen, Egyetem tér 1, Debrecen, H-4032, Hungary Export Date: 22 March 2024 Correspondence Address: Tuba, R.; Institute of Materials and Environmental Chemistry, Magyar tudósok körútja 2, Hungary; email: tuba.robert@ttk.hu AB - Isomerization Metathesis (ISOMET) reaction is an emerging tool for “open loop” chemical recycling of polyethylene to propylene. Novel, latent N ‐Alkyl substituted Cyclic(Alkyl)(Amino)Carbene (CAAC)–ruthenium catalysts ( 5a‐Ru , 3b‐Ru – 6c‐Ru ) are developed rendering “inverted” chemical structure while showing enhanced ISOMET activity in combination with (RuHCl)(CO)(PPh 3 ) 3 ( RuH ) double bond isomerization co‐catalyst. Systematic investigations reveal that the steric hindrance of the substituents on nitrogen and carbon atom adjacent to carbene moiety in the CAAC ligand have significantly improved the catalytic activity and robustness. In contrast to the NHC‐Ru and CAAC‐Ru catalyst systems known so far, these systems show higher isomerization metathesis (ISOMET) activity (TON: 7400) on the model compound 1‐octadecene at as low as 3.0 bar optimized pressure, using technical grade (3.0) ethylene. The propylene content formed in the gas phase can reach up to 20% by volume. LA - English DB - MTMT ER - TY - JOUR AU - Molnár, Márk AU - Balázs, Barbara AU - Bényei, Attila Csaba AU - Nyerges, Miklós TI - Diastereoselective cycloaddition of isatin derived azomethine ylides to 3-nitro-2(1H)-quinolones JF - TETRAHEDRON J2 - TETRAHEDRON VL - 153 PY - 2024 PG - 7 SN - 0040-4020 DO - 10.1016/j.tet.2024.133848 UR - https://m2.mtmt.hu/api/publication/34558201 ID - 34558201 LA - English DB - MTMT ER - TY - JOUR AU - Császár, Zsófia AU - Pőrgye, Zsanett E. AU - Farsang, Evelin AU - Kovács, Margit AU - Bényei, Attila Csaba AU - Bakos, József AU - Farkas, Gergely TI - Ruthenium complexes of new chiral phosphine‐amine‐ether ligands (Ru‐PNO) for asymmetric hydrogenation – the role of backbone chirality in pincer ligand design JF - APPLIED ORGANOMETALLIC CHEMISTRY J2 - APPL ORGANOMET CHEM PY - 2024 SN - 0268-2605 DO - 10.1002/aoc.7379 UR - https://m2.mtmt.hu/api/publication/34555466 ID - 34555466 AB - New chiral phosphine‐amine‐ether (PNO) ligands of the general formula Ph 2 PCH(R 1 )(CH 2 ) n CH(R 1 )N(R 2 )CH(R 3 )CH 2 OMe, where R 1 , R 2 , and R 3 = H or Me, n = 0 or 1, and their ruthenium complexes of the type [RuCl 2 (PPh 3 )(PNO)] have been synthesized. The coordination compounds were characterized by 1D and 2D NMR spectroscopy, modeled by DFT calculations, and in one case analyzed by X‐ray crystallography. The combined spectroscopic and theoretical investigations revealed that the relative configuration of the stereogenic elements in the P–N and N–O backbone represents a crucial factor in determining the conformation of the pincer‐type chelates and may also affect the configuration of the coordinated stereogenic nitrogen in the NH subunit, an essential element of stereochemical communication in outer sphere bifunctional catalysis. The new complexes were applied in the asymmetric hydrogenation of fused ring bicyclic ketones (i.e., 1‐tetralone and 4‐chromanone derivatives), a challenging substrate class, where enantioselectivities up to 97% could be obtained. Based on the spectroscopic and theoretical studies and catalytic experiments, structural features affecting the stereochemistry of the coordination could be identified and a qualitative enantioinduction model has been proposed. LA - English DB - MTMT ER - TY - JOUR AU - Chniti, Sami AU - Pongrácz, Péter AU - Kollár, László AU - Bényei, Attila Csaba AU - Dörnyei, Ágnes AU - Takács, Attila TI - Synthesis of Chroman-2,4-diones via Ring-Opening/Ring-Closing Reaction Involving Palladium-Catalyzed Intramolecular Aryloxycarbonylation JF - JOURNAL OF ORGANIC CHEMISTRY J2 - J ORG CHEM VL - 89 PY - 2024 IS - 2 SP - 1175 EP - 1183 PG - 9 SN - 0022-3263 DO - 10.1021/acs.joc.3c02337 UR - https://m2.mtmt.hu/api/publication/34492221 ID - 34492221 AB - Palladium-catalyzed aminocarbonylation of 3-iodochromone was studied in the presence of primary and secondary amines using atmospheric pressure of carbon monoxide as a carbonyl source. This procedure successfully provided a library of chromone-3-carboxamides and 3-substituted chroman-2,4-diones in 40 to 92% isolated yields. The reaction proceeded via highly chemoselective aminocarbonylation (up to 100%) in the presence of secondary amines by using monodentate or bidentate phosphine ligands. The tendency of 3-iodochromone substrate to undergo ANRORC rearrangement with N-nucleophiles was crucial to shift the reaction toward an unprecedented chemoselective carbonylative transformation, where a late-stage carbonyl insertion is favored concomitantly to the last ring-closure step. The proposed azaMichael addition/ring-opening/intramolecular aryloxycarbonylation sequence showed compatibility, uniquely, to primary amines when XantPhos was used as a ligand. The solid-state structures of chromone-3-carboxamide (2a) and chroman-2,4-dione (3s) were undoubtedly established by single-crystal XRD analysis. A catalytic cycle was proposed to rationalize the formation of the two types of carbonylated compounds. LA - English DB - MTMT ER - TY - JOUR AU - Farkas, Gergely AU - Császár, Zsófia AU - Farsang, Evelin AU - Bényei, Attila Csaba AU - Bakos, József TI - Application of alkane-diyl based chiral phosphine-aminophosphine (P-NP) and thioether-aminophosphine (S-NP) ligands in Rh-catalyzed asymmetric hydrogenation JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY J2 - J ORGANOMET CHEM VL - 994 PY - 2023 SN - 0022-328X DO - 10.1016/j.jorganchem.2023.122723 UR - https://m2.mtmt.hu/api/publication/33785458 ID - 33785458 LA - English DB - MTMT ER - TY - JOUR AU - Kacsir, István AU - Sipos, Adrienn AU - Major, Evelin AU - Bajusz, Nikolett AU - Bényei, Attila Csaba AU - Buglyó, Péter AU - Somsák, László AU - Kardos, Gábor AU - Bay, Péter AU - Bokor, Éva TI - Half-Sandwich Type Platinum-Group Metal Complexes of C-Glucosaminyl Azines: Synthesis and Antineoplastic and Antimicrobial Activities JF - MOLECULES J2 - MOLECULES VL - 28 PY - 2023 IS - 7 PG - 50 SN - 1420-3049 DO - 10.3390/molecules28073058 UR - https://m2.mtmt.hu/api/publication/33734265 ID - 33734265 N1 - Funding details: NKM2022-30, POST-COVID2021-33 Funding details: Magyar Tudományos Akadémia, MTA Funding details: Debreceni Egyetem, DE, TKP2020-IKA-04, TKP2021-EGA-19, TKP2021-EGA-20 Funding details: Nemzeti Kutatási Fejlesztési és Innovációs Hivatal, NKFIH, FK125067, K142141 Funding text 1: Our work was supported by the National Research, Development and Innovation Office of Hungary (grants K142141 and FK125067), by the University of Debrecen, by the Thematic Excellence Programme (TKP2020-IKA-04, TKP2021-EGA-19, TKP2021-EGA-20) of the Ministry for Innovation and Technology in Hungary and by the Momentum fellowship and POST-COVID2021-33 and NKM2022-30 grants of the Hungarian Academy of Sciences. AB - While platinum-based compounds such as cisplatin form the backbone of chemotherapy, the use of these compounds is limited by resistance and toxicity, driving the development of novel complexes with cytostatic properties. In this study, we synthesized a set of half-sandwich complexes of platinum-group metal ions (Ru(II), Os(II), Ir(III) and Rh(III)) with an N,N-bidentate ligand comprising a C-glucosaminyl group and a heterocycle, such as pyridine, pyridazine, pyrimidine, pyrazine or quinoline. The sugar-containing ligands themselves are unknown compounds and were obtained by nucleophilic additions of lithiated heterocycles to O-perbenzylated 2-nitro-glucal. Reduction of the adducts and, where necessary, subsequent protecting group manipulations furnished the above C-glucosaminyl heterocycles in their O-perbenzylated, O-perbenzoylated and O-unprotected forms. The derived complexes were tested on A2780 ovarian cancer cells. Pyridine, pyrazine and pyridazine-containing complexes proved to be cytostatic and cytotoxic on A2780 cells, while pyrimidine and quinoline derivatives were inactive. The best complexes contained pyridine as the heterocycle. The metal ion with polyhapto arene/arenyl moiety also impacted on the biological activity of the complexes. Ruthenium complexes with p-cymene and iridium complexes with Cp* had the best performance in ovarian cancer cells, followed by osmium complexes with p-cymene and rhodium complexes with Cp*. Finally, the chemical nature of the protective groups on the hydroxyl groups of the carbohydrate moiety were also key determinants of bioactivity; in particular, O-benzyl groups were superior to O-benzoyl groups. The IC50 values of the complexes were in the low micromolar range, and, importantly, the complexes were less active against primary, untransformed human dermal fibroblasts; however, the anticipated therapeutic window is narrow. The bioactive complexes exerted cytostasis on a set of carcinomas such as cell models of glioblastoma, as well as breast and pancreatic cancers. Furthermore, the same complexes exhibited bacteriostatic properties against multiresistant Gram-positive Staphylococcus aureus and Enterococcus clinical isolates in the low micromolar range. LA - English DB - MTMT ER - TY - JOUR AU - Le Khanh, Ha Pham AU - Haimhoffer, Ádám AU - Nemes, Dániel AU - Józsa, Liza AU - Vasvári, Gábor AU - Budai, István AU - Bényei, Attila Csaba AU - Ujhelyi, Zoltán AU - Siposné Fehér, Pálma AU - Bácskay, Ildikó TI - Effect of Molecular Weight on the Dissolution Profiles of PEG Solid Dispersions Containing Ketoprofen JF - POLYMERS J2 - POLYMERS-BASEL VL - 15 PY - 2023 IS - 7 SP - 1 EP - 15 PG - 15 SN - 2073-4360 DO - 10.3390/polym15071758 UR - https://m2.mtmt.hu/api/publication/33727451 ID - 33727451 AB - Solid dispersions are typically binary systems with a hydrophilic matrix polymer and a lipophilic active substance. During formulation, the drug undergoes a crystalline to amorphous phase transition, which leads to a supersaturated solution providing enhanced bioavailability. The interaction of the active substance and the polymer is unique and influences the level of supersaturation. We aimed to investigate the relationship between low molecular weight polyethylene glycol derivates PEG 1000, 1500, and 2000 and ketoprofen regarding the effect of molecular weight. The physicochemical properties of solid dispersions prepared with hot melt homogenization and their respective physical mixtures were investigated with Fourier transform infrared spectroscopy, powder X-ray diffraction and scanning electron microscopy techniques. A phase solubility study was carried out in hydrochloric acid media which showed no difference between the three polymers, but the dissolution curves differed considerably. PEG 1000 had higher percentage of released drug than PEG 1500 and 2000, which had similar results. These results indicate that when multiple low molecular weight PEGs are suitable as matrix polymers of solid dispersions, the molecular weight has only limited impact on physicochemical characteristics and interactions and further investigation is needed to select the most applicable candidate. LA - English DB - MTMT ER - TY - JOUR AU - Király, Sándor Balázs AU - Tóth, László AU - Kovács, Tibor AU - Bényei, Attila Csaba AU - Lisztes, Erika AU - Tóth, Balázs István AU - Bíró, Tamás AU - Kiss, Attila AU - E Kövér, Katalin AU - Mándi, Attila AU - Kurtán, Tibor TI - Multifaceted Domino Knoevenagel‐Cyclization Reactions; Four Movements for 2H‐Chromenes and Chromans JF - ADVANCED SYNTHESIS & CATALYSIS J2 - ADV SYNTH CATAL VL - 365 PY - 2023 IS - 19 SP - 3301 EP - 3319 PG - 19 SN - 1615-4150 DO - 10.1002/adsc.202300083 UR - https://m2.mtmt.hu/api/publication/33683947 ID - 33683947 AB - Domino Knoevenagel-cyclization reactions of 2H-chromene and chroman derivatives containing o-formylaryl amine or ether side-chain was carried out to produce four series of chiral condensed heterocycles representing four novel skeletons and exhibiting antiproliferative activity. The cyclization step occurred with four different mechanisms: a concerted intramolecular hetero Diels-Alder reaction (IMHDA), a stepwise polar [2+2] cycloaddition, a [1,5]-hydride shift-6-endo cyclization or a multi-step nitro hetero Diels-Alder-ring-opening-Cadogan-type cyclization sequence. The latter reaction provided a new route to hydroxyindoles by an inverse Cadogan-type cyclization, in which the nitro group is deoxygenated by a nitro IMHDA-ring-opening sequence. The cyclization mechanisms and their stereoselectivity were studied by DFT calculations, based on which we proposed a mechanism for the multi-step cyclization to hydroxyindoles and explained the observed diastereoselectivity. LA - English DB - MTMT ER - TY - JOUR AU - Bege, Miklós AU - Herczeg, Mihály AU - Bakai-Bereczki, Ilona AU - Debreczeni, Nóra AU - Bényei, Attila Csaba AU - Herczegh, Pál AU - Borbás, Anikó TI - Triaza-tricyclanos – synthesis of a new class of tricyclic nucleoside analogues by stereoselective cascade cyclocondensation JF - ORGANIC & BIOMOLECULAR CHEMISTRY J2 - ORG BIOMOL CHEM VL - 21 PY - 2023 IS - 10 SP - 2213 EP - 2219 PG - 7 SN - 1477-0520 DO - 10.1039/D3OB00154G UR - https://m2.mtmt.hu/api/publication/33657380 ID - 33657380 AB - Conformationally constrained tricyclic morpholino-nucleosides containing three new chirality centers were prepared with full stereoselectivity, through two consecutive hemiaminal-imidazolidine cascade reactions. LA - English DB - MTMT ER -