engleski

Catalyzed carboxylative C-C cross coupling reactions of propargyl alcohols

Catalyzed carboxylative C-C cross coupling reactions of propargyl alcohols Maria Kolympadi Markovic, a Filip Vranješević, b Dario Matulja, b Marija Jozanović, c Nikola Sakač, d Gabriela Ambrožić, a Davor Šakić, e Valerije Vrček, e and Dean Marković*b a University of Rijeka, Faculty of Physics, and Centre for Micro- and Nanosciences and Technologies, R. Matejčić 2, 51000 Rijeka, Croatia b University of Rijeka, Department of Biotechnology, R. Matejčić 2, 51000 Rijeka, Croatia c University of Osijek, Department of Chemistry, C. Hadrijana 8/A, 31000 Osijek, Croatia d University of Zagreb, Faculty of Geotechnical Engineering, Hallerova aleja 7, 42000 Varaždin, Croatia e University of Zagreb, Faculty of Pharmacy and Biochemistry, A. Kovačića 1, 10000 Zagreb, Croatia E-mail: maria.kolympadi@uniri.hr Valorization of carbon dioxide (CO2) gas as C1 building block for producing highly valued and biologically active chemicals following the principles of green chemistry represents a current challenge in modern organic synthesis.1 Metal catalyzed CO2 capture by propargylic substrates -alcohols or amines- affords α-alkylidene cyclic carbonates or carbamates, respectively.2 Domino reactions that combine CO2 capture followed by a C-C cross-coupling reaction may give direct access to complex products that otherwise require multistep syntheses.3 We have accordingly envisaged energetically favored Pd-catalyzed intermolecular or intramolecular C-C cross-coupling reactions on suitable propargylic alcohol substrates, which can overcome the thermodynamic and kinetic stability of CO2. Notably, our calculations based on density functional theory (DFT) method predict that these reactions are exergonic owned to product stabilization through the formation of additional C-C bonds. We are currently examining the role of additives, such as Cu salts, which are mediating the Pd catalysis, probably due to their reducing and complexing properties, and increase the reaction yields under atmospheric pressure of CO2. Our combined studies -experimental and computational- enable the rational design of new CO2 trapping substrates and the preparation of useful fine chemicals such as cyclic carbonates. Acknowledgements: Croatian Science Foundation (INDICATIOR, IP-2019-04-8846) ; University of Rijeka (uniri-prirod-18-102-1237). 1 Q. Liu, L. Wu, R. Jackstell, M. Beller, Nat. Commun. 2015, 6, 5933. 2 F. Vranješević, M. Kolympadi Markovic, D. Matulja, G. Ambrožić, J.Á. Sordo, S. Laclef, V. Vrček, D. Marković, Catalysts 2022, 12(5), 547. 3 P. García-Domínguez, L. Fehr, G. Rusconi, C. Nevado, Chem. Sci. 2016, 7, 3914 ; S. Sun, B. Wang, N. Gu, J.-T. Yu, J. Cheng, Org. Lett. 2017, 19, 1088.

carbon dioxide¸ cyclic carbonates, in-silico studies, catalysis

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