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 - Carrilho, Rui M. B. AU - Calvete, Mário J. F. AU - Mikle, Gábor AU - Kollár, László AU - Pereira, Mariette M. TI - Carbon monoxide as a C1 building block in fine chemical synthesis JF - CHINESE JOURNAL OF CHEMISTRY J2 - CHINESE J CHEM VL - 42 PY - 2024 IS - 2 SP - 199 EP - 221 PG - 23 SN - 1001-604X DO - 10.1002/cjoc.202300384 UR - https://m2.mtmt.hu/api/publication/34225873 ID - 34225873 N1 - Funding Agency and Grant Number: Portuguese Agency for Scientific Research "Fundaco para a Ciencia e a Tecnologia" (FCT) [COMPETE2020-UE, UIDB/00070/ 2020, UIDP/00070/2020, UIDB/00313/2020, UIDP/00313/2020, UIDB/00285/2020]; MTA Distinguished Guest Scientist Fellowship 2023 grant; NKFIH [TKP2021-EGA-17] Funding text: The authors acknowledge Portuguese Agency for Scientific Research "Fundac & atilde;o para a Ciencia e a Tecnologia" (FCT) and COMPETE2020-UE, for funding through projects UIDB/00070/ 2020, UIDP/00070/2020, UIDB/00313/2020, UIDP/00313/2020 and UIDB/00285/2020 to Coimbra Chemistry Centre (CQC). M.M. Pereira thanks MTA Distinguished Guest Scientist Fellowship 2023 grant. L. Kollar thanks to NKFIH for funding through project TKP2021-EGA-17. AB - Carbon monoxide (CO) has become one of the most relevant and versatile renewable C1 building blocks for chemical synthesis, especially in the fine chemicals industry, due to the development of efficient and selective catalysts for its activation. In this review, we present a comprehensive critical analysis of the last 10 years literature on the use of CO as a renewable feedstock for fine chemicals production. The review is organized by type of catalytic reaction, namely alkene and alkyne carbonylation, hydroformylation, carbonylation of aryl halides, carbonylative cross‐coupling and C–H carbonylation. Notable examples of the synthesis of relevant building blocks and/or known pharmaceuticals are highlighted. Emphasis is placed on examples of utilizing CO as the C1 building block in one or more catalytic steps. The catalyst used and the reaction conditions are consistently presented throughout all of the examples. LA - English DB - MTMT ER - TY - CHAP AU - Bencze, Flórián AU - Bognár, Balázs AU - Kálai, Tamás AU - Kollár, László AU - Nagymihaly, Zoltan AU - Kunsági-Máté, Sándor ED - Hagymási, Krisztina ED - Janda, Tibor ED - Pál, Magda ED - Poór, Péter ED - Szalai, Gabriella TI - Kettős (Spin és Fluoreszcens) Szenzor Molekulák Új Alkalmazása T2 - A Magyar Szabadgyökkutató Társaság XII. Kongresszusa PB - Agrártudományi Kutatóközpont, Mezőgazdasági Intézet CY - Martonvásár SN - 9786156203021 PY - 2023 SP - 13 EP - 13 PG - 1 UR - https://m2.mtmt.hu/api/publication/34131883 ID - 34131883 LA - English DB - MTMT ER - TY - JOUR AU - Kollár, László AU - Takács, Attila AU - Molnár, Csilla AU - Kovács, Andrew AU - Mika, László Tamás AU - Pongrácz, Péter TI - Palladium-Catalyzed Selective Amino- and Alkoxycarbonylation of Iodoarenes with Aliphatic Aminoalcohols as Heterobifunctional O,N-Nucleophiles JF - JOURNAL OF ORGANIC CHEMISTRY J2 - J ORG CHEM VL - 88 PY - 2023 IS - 8 SP - 5172 EP - 5179 PG - 8 SN - 0022-3263 DO - 10.1021/acs.joc.2c02712 UR - https://m2.mtmt.hu/api/publication/33752587 ID - 33752587 N1 - Funding Agency and Grant Number: Hungarian National Research, Development and Innovation Office [K 113177, K 128473, FK 143197, GINOP-2.3.2-15-2016-00049]; NKFIH [TKP2021-EGA-02, TKP2021-EGA-17]; European Union; European Social Fund [EFOP-3.6.1.-16-2016-00004] Funding text: The authors thank the Hungarian National Research, Development and Innovation Office (Grants K 113177, K 128473, and FK 143197 and Grant GINOP-2.3.2-15-2016-00049), for the financial support. The research in Hungary was funded by NKFIH within the framework of Projects TKP2021-EGA-02 and TKP2021-EGA-17. The project has also been supported by the European Union, co-financed by the European Social Fund Grant EFOP-3.6.1.-16-2016-00004 entitle Comprehensive Development for Implementing Smart Specialization Strategies at the University of Pecs. AB - Palladium-catalyzed amino-and alkoxycarbonyla-tion reactions of aryl iodides were investigated in the presence of aliphatic heterobifunctional N,O-nucleophiles. Selective synthesis of amide alcohols and amide esters was realized, controlled by the base and substrate ratio. The effect of iodobenzene substituents was also studied with surprising results in terms of product selectivity. In addition to the model ethanolamine/iodobenzene system, various heteroaromatic substrates and numerous related nucleophiles were tested under optimized conditions, providing moderate to good yields of the target compounds. Reactions of serinol and 1,3-diamino-2-propanol as model trifunctional compounds showed particularly high chemoselectivity on amide ester products. Considering the coordinative properties of the applied nucleophiles, a rational catalytic cycle was proposed. LA - English DB - MTMT ER - TY - JOUR AU - Bencze, Flórián AU - Bognár, Balázs AU - Kálai, Tamás AU - Kollár, László AU - Nagymihaly, Zoltan AU - Kunsági-Máté, Sándor TI - A New Application of Spin and Fluorescence Double-Sensor Molecules JF - MOLECULES J2 - MOLECULES VL - 28 PY - 2023 IS - 7 PG - 12 SN - 1420-3049 DO - 10.3390/molecules28072978 UR - https://m2.mtmt.hu/api/publication/33722185 ID - 33722185 AB - EPR imaging techniques are known to be successful tools for mapping living bodies, especially because of the high transparency of tissues in the microwave range. This technique assumes the presence of radicals whose in vivo transport is also controlled by serum albumins. Accordingly, in this study, the interactions between 3-hydroxymethyl-1-oxyl-4-(pyren-1-yl)-2,2,5,5-tetramethyl-2,5-dihydro-1H-pyrrole radical and the human serum albumin molecules were investigated. To clarify the adsorption processes of this radical onto the surface of human serum albumin (HSA), the interaction of the OMe derivative of the radical was also examined parallel with the studies on the radical—HSA interactions. Considering the solubility issues and also to modulate the transport, inclusion complexes of the radical with a cavitand derivative were also studied. The latter interactions were observed through fluorescence spectroscopy, fluorescence polarization, and by EPR spectroscopy. As a double-sensor molecule, we found that the fluorophore nitroxide is a good candidate as it gave further information about host-guest interactions (fluorescence, fluorescence polarization, and EPR). We also found that in the presence of a cavitand, a complex with greater stability was formed between the sensor molecule and the human serum albumin. Based on these observations, we can conclude that applying this double-sensor (spin, fluorescent) molecule is useful in cases when different interactions can affect the EPR measurements. LA - English DB - MTMT ER - TY - JOUR AU - Chniti, S. AU - Kollár, László AU - Bényei, Attila Csaba AU - Dörnyei, Ágnes AU - Takács, Attila TI - Highly Chemoselective One-Step Synthesis of Novel N-Substituted-Pyrrolo[3,4-b]quinoline-1,3-diones via Palladium-Catalyzed Aminocarbonylation/Carbonylative Cyclisation Sequence JF - EUROPEAN JOURNAL OF ORGANIC CHEMISTRY J2 - EUR J ORG CHEM VL - 26 PY - 2023 IS - 10 SN - 1434-193X DO - 10.1002/ejoc.202201374 UR - https://m2.mtmt.hu/api/publication/33649520 ID - 33649520 N1 - Funding Agency and Grant Number: NKFIH [TKP2021-EGA-17]; National Research, Development, and Innovation Office [PD-132403]; National Research, Development and Innovation Fund of Hungary [TKP2020-4.1.1] Funding text: The research in Hungary was funded by NKFIH within the framework of the project TKP2021-EGA-17. This research was financed by the National Research, Development, and Innovation Office (Grant Number PD-132403). Project no. TKP2020-4.1.1 has been implemented with the support provided from the National Research, Development and Innovation Fund of Hungary, financed under the Thematic Excellence Program 2020 National Excellence Sub-program. The authors are grateful to Gabor Mikle and Peter Pongracz for the help in optical rotation measurements. The research was performed in collaboration with the Mass Spectrometry Core Facility at the Szentagothai Research Centre of the University of Pecs. AB - Novel N-substituted pyrrolo[3,4-b]quinoline-1,3-diones have been prepared via a highly chemoselective palladium-catalyzed carbonylative imidazation-cyclization reaction in a one-pot synthetic approach. This methodology, which has been applied for the first time to access such original scaffolds through two different protocols involving 3-bromo-2-iodoquinoline, as a typical partner, primary amines, and atmospheric or high carbon monoxide pressure (20 bar), has shown an excellent tolerance for many functional groups. The use of bidentate ligands such as XantPhos and dppp, either under atmospheric or high-pressure conditions, provides a wide range of carbonylated compounds in good to excellent yields (up to 82 %). Furthermore, some new quinoline-2,3-dicarboxamides have been isolated as side products in very low yields and have been fully characterized. The solid state structures of three of the synthesized acridinimides have been unequivocally established by single-crystal XRD analysis. © 2023 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH. LA - English DB - MTMT ER - TY - JOUR AU - Bede, Fanni AU - Mahó, Sándor AU - Sándor, Viktor AU - Mikle, Gábor AU - Kollár, László TI - Carboxamide formation in less favoured positions: Facile synthesis of 7-carboxamidochenodeoxycholanic acid derivatives JF - TETRAHEDRON J2 - TETRAHEDRON VL - 133 PY - 2023 PG - 4 SN - 0040-4020 DO - 10.1016/j.tet.2023.133292 UR - https://m2.mtmt.hu/api/publication/33636217 ID - 33636217 N1 - Funding Agency and Grant Number: NKFIH, Hungary [TKP2021-EGA-17] Funding text: The research was funded by NKFIH, Hungary within the framework of the project TKP2021-EGA-17. LA - English DB - MTMT ER - TY - JOUR AU - Szuroczki, Péter AU - Takátsy, A. AU - Csók, Zsolt AU - Kégl, Tímea AU - Kollár, László TI - Unexpected selectivities in transition metal-catalyzed hydroformylation of vinyl-substituted cavitands JF - MOLECULAR CATALYSIS J2 - MOL CATAL VL - 535 PY - 2023 PG - 5 SN - 2468-8231 DO - 10.1016/j.mcat.2022.112837 UR - https://m2.mtmt.hu/api/publication/33573010 ID - 33573010 LA - English DB - MTMT ER - TY - JOUR AU - Uzunlu, N. AU - Pongrácz, Péter AU - Kollár, László AU - Takács, Attila TI - Alkyl Levulinates and 2-Methyltetrahydrofuran: Possible Biomass-Based Solvents in Palladium-Catalyzed Aminocarbonylation JF - MOLECULES J2 - MOLECULES VL - 28 PY - 2023 IS - 1 PG - 15 SN - 1420-3049 DO - 10.3390/molecules28010442 UR - https://m2.mtmt.hu/api/publication/33570635 ID - 33570635 AB - In this research, ethyl levulinate, methyl levulinate, and 2-methyltetrahydrofuran as bio-derived hemicellulose-based solvents were applied as green alternatives in palladium-catalyzed aminocarbonylation reactions. Iodobenzene and morpholine were used in optimization reactions under different conditions, such as temperatures, pressures, and ligands. It was shown that the XantPhos ligand had a great influence on conversion (98%) and chemoselectivity (100% carboxamide), compared with the monodentate PPh3. Following this study, the optimized conditions were used to extend the scope of substrates with nineteen candidates (various para-, ortho-, and meta-substituted iodobenzene derivatives and iodo-heteroarenes), as well as eight different amine nucleophiles. © 2023 by the authors. LA - English DB - MTMT ER - TY - JOUR AU - Kiss, László AU - Nagymihaly, Zoltan AU - Kollár, László AU - Kunsági-Máté, Sándor TI - Voltammetric and Fluorimetric Studies of Dibenzoylmethane on Glassy Carbon Electrodes and Its Interaction with Tetrakis (3,5-Dicarboxyphenoxy) Cavitand Derivative JF - MOLECULES J2 - MOLECULES VL - 28 PY - 2023 IS - 1 PG - 9 SN - 1420-3049 DO - 10.3390/molecules28010185 UR - https://m2.mtmt.hu/api/publication/33550159 ID - 33550159 AB - Due to the medical importance of dibenzoylmethane, one of the aims of the study was to find an appropriate packing material and a biologically friendly co-solvent to help its introduction into living systems. Accordingly, redox properties of dibenzoylmethane were investigated on glassy carbon electrodes in acetonitrile and in 1-propanol with cyclic voltammetry, and showed a diffusion-controlled process. In the anodic window, an oxidation peak appeared at around 1.9 V in both solvents. Cycling repeatedly between 0 and 2 V, the reproducibility of this peak was acceptable, but when extending the window to higher potentials, the electrode deactivated, obviously due to electrode material. The addition of the investigated tetrakis(3,5-dicarboxyphenoxy) cavitand did not significantly change the voltammograms. Further electrochemical experiments showed that the coexistence of water in acetonitrile and 1-propanol drastically reduces the solubility of dibenzoylmethane. Moreover, very rapid electrode deactivation occurred and this fact made the use of electrochemical methods complicated. Considering that both the cavitand and dibenzoylmethane are soluble in dimethyl sulfoxide, the interaction of these species was investigated and formation of stable complexes was detected. This observation was verified with fluorescence quenching studies. The mixture of water and dimethyl sulphoxide also dramatically improved the solubility of the cavitand–dibenzoylmethane complex at high excess of water. The addition of cavitand improved the solubility of dibenzoylmethane, a property which supports the application of dibenzoylmethane in therapy. LA - English DB - MTMT ER -