Chair of Organic chemistry

Sustainable chemistry

Targeted solvent design

Ionic liquids (ILs) are salts that melt at relatively low temperatures, often below 0 °C. Being ionic compounds, they are extremely non-volatile, but still fluid. Estimates suggest around one million of distinct ionic liquids can be obtained by combining various cations and anions. This paves the way for designing liquids that can serve a particular function, e.g., as solvents for certain type of organic transformations or as electrolytes for power storage and conversion.

In our lab, we combine the expertise on high quality custom-ionic liquid synthesis with a targeted structural IL advancement for enabling these unique materials to improve chemical processes' efficiency and sustainability. Our research is focused on understanding the underlying design principles for ionic liquids that would contribute to reaching the said goals by, e.g., improving the energy consumption of chemicals’ synthesis, improving the energy consumption of gas mixture separation, reducing the use of organic solvents, which are volatile organic compounds (VOCs), ensuring a non-flammable media for chemical transformations.

Continuous flow electrochemistry and asymmetric organocatalytic transformations in flow.

Flow chemistry involves conducting reactions in the continuous flow of the reagents or their solution. Main advantages of the flow chemistry as compared to the batch reaction mode are enhanced safety, improved heat transfer and better temperature control, accelerated reaction rates, improved selectivity and great potential for manufacturing scale-out. Furthermore, the use of small reaction mixture volumes in flow chemistry enables the efficient identification of optimal parameters for a given chemical transformation. This streamlined process significantly reduces the amount of starting materials required, allowing for faster experimentation and discovery of ideal reaction conditions.
Our research is focused on continuous flow electrochemistry and the development of asymmetric organocatalytic transformations in flow.

Project tittle: Synthesis, Structure and Properties of Novel Silicon-based Ionic Liquids: Towards Targeted Solvent Engineering

Project number: 1.1.1.2/VIAA/3/19/549

Project partners:

• Laboratoire de Chimie ENS De Lyon (FR), Prof. Margarida Costa Gomes
• University of Porto (PT), Prof. Luis Santos
• The University of Auckland (NZ), Sen. Lect. Cameron Charles Weber

Project implementation timeline: 01.02.2020. – 31.01.2023.
Project leader: Principal Researcher, Dr. Chem. Eduards Bakis

List of publications

Kluga, R.; Kinens, A.; Suna, E. "Chiral 4-MeO-Pyridine (MOPY) Catalyst for Enantioselective Cyclopropanation: Attenuation of Lewis Basicity Leads to Improved Catalytic Efficiency." Chem. Eur. J. 2024, e202301136, DOI: 10.1002/chem.202301136

Koleda O., Prane K., Suna E. "Electrochemical Synthesis of Unnatural Amino Acids via Anodic Decarboxylation of N-Acetylamino Malonic Acid Derivatives" Org. Lett. 2023, DOI: 10.1021/acs.orglett.3c02687

Mohebbati, N.; Sokolovs, I.; Woite, P.; Lõkov, M.; Parman, E.; Ugandi, M.; Leito, I.; Roemelt, M.; Suna, E.; Francke, R. "Electrochemistry and Reactivity of Chelation-stabilized Hypervalent Bromine(III) Compounds" Chem.Eur. J. 2022, 28, e2022009. DOI: 10.1002/chem.202200974

Bobiļeva, O.; Bobrovs, R.; Kaņepe, I.; Patetko, L.; Kalniņš, G.; Šišovs, M.; Bula, A.L.; Grīnberga, S.; Borodušķis, M.; Ramata-Stunda, A.; Rostoks, N.; Jirgensons, A.; Tārs, K.; Jaudzems K. "Potent SARS-CoV-2 mRNA Cap Methyltransferase Inhibitors by Bioisosteric Replacement of Methionine in SAM Cosubstrate" ACS Med. Chem. Lett. 2021, 12, 1102–1107. DOI: 10.1021/acsmedchemlett.1c00140

Fridmanis, J.; Otikovs, M.; Brangulis, K.; Tārs, K.; Jaudzems, K. "Solution NMR structure of Borrelia burgdorferi outer surface lipoprotein BBP28, a member of the mlp protein family" Proteins 2021, 89, 588–594. DOI: 10.1002/prot.26011

Brune, K. D.; Liekniņa, I.; Sutov, G.; Morris, A. R.; Jovicevic, D.; Kalniņš, G.; Kazāks, A.; Kluga, R.; Kastaljana, S.; Zajakina, A.; Jansons, J.; Skrastiņa, D.; Spunde, K.; Cohen, A. A.; Bjorkman, P. J.; Morris, H. R.; Suna, E.; Tārs, K. "N-Terminal Modification of Gly-His-Tagged Proteins with Azidogluconolactone" ChemBioChem 2021, 22, 3199-3207. DOI: 10.1002/cbic.202100381

Sokolovs, I.; Mohebbati, N.; Francke, R.; Suna, E. "Electrochemical Generation of Hypervalent Bromine(III) Compounds" Angew. Chem. Int. Ed. 2021, 60, 15832–15837. DOI: 10.1002/anie.202104677

Gulbe, K.; Lugiņina, J.; Jansons, E.; Kinens, A.; Turks, M. "Metal-free glycosylation with glycosyl fluorides in liquid SO₂" Beilstein J. Org. Chem. 2021, 17, 964-976. DOI: 10.3762/bjoc.17.78

Kinens, A.; Balkaitis, S.; Ahmad, O. K.; Piotrowski, D. W.; Suna, E. "Acylative Dynamic Kinetic Resolution of Secondary Alcohols: Tandem Catalysis by HyperBTM and Bäckvall’s Ruthenium Complex" J. Org. Chem. 2021, 86, 7189–7202. DOI: 10.1021/acs.joc.1c00545

Bakis, E.; van den Bruinhorst, A.; Pison, L.; Palazzo, I.; Chang, T.; Kjellberg, M.; Weber, Cameron C.; Gomes, Margarida C.; Welton, T. "Mixing divalent ionic liquids: effects of charge and side-chains" Phys. Chem. Chem. Phys. 2021, 23, 4624-4635. DOI: 10.1039/D1CP00208B

Jaudzems, K.; Kurbatska, V.; Jēkabsons, A.; Bobrovs, R.; Rudevica, Z.; Leonchiks, A. "Targeting Bacterial Sortase A with Covalent Inhibitors: 27 New Starting Points for Structure-Based Hit-to-Lead Optimization" ACS Infect. Dis. 2020, 6, 186-194. DOI: 10.1021/acsinfecdis.9b00265

Kinens, A.; Balkaitis, S.; Suna, E. "Preparative-Scale Synthesis of Vedejs Chiral DMAP Catalysts" J. Org. Chem. 2018, 83, 12449–12459. DOI: 10.1021/acs.joc.8b01687

Kinens, A.; Sejejs, M.; Kamlet, A. S.; Piotrowski, D. W.; Vedejs, E.; Suna, E. "Development of a Chiral DMAP Catalyst for the Dynamic Kinetic Resolution of Azole Hemiaminals" J. Org. Chem. 2017, 82, 869–886. DOI: 10.1021/acs.joc.6b02955

Koleda, O.; Broese, T.; Noetzel, J.; Roemelt, M.; Suna, E.; Francke, R. "Synthesis of Benzoxazoles Using Electrochemically Generated Hypervalent Iodine" J. Org. Chem. 2017, 82, 11669–11681. DOI: 10.1021/acs.joc.7b01686

Priede, E.; Brica, S.; Bakis, E.; Udris, N.; Zicmanis, A. "Ionic liquids as solvents for the Knoevenagel condensation: understanding the role of solvent–solute interactions" New J. Chem. 2015, 39, 9132–9142. DOI: 10.1039/C5NJ01906K

Priede, E.; Bakis, E.; Zicmanis, A. "When Chlorides are the Most Reactive: A Simple Route towards Diverse Mono- and Dicationic Dimethyl Phosphate Ionic Liquids" Synlett. 2014, 17, 2447-2450. DOI: 10.1055/s-0034-1379018