Asümmeetrilise oksüdatsiooni töörühm
Klassifikaator (Frascati)
Uurimisrühma juht
Uurimisrühma liige
Doktorant
Võtmesõna
asümmeetriline keemiline süntees
bioaktiivsete ühendite süntees
Ülevaade
Uurimused on tihedalt seotud Molekulaarse Rakutehnoloogia Tippkeskuse tematikaga (Center of Excellence in Molecular Cell Engineering, CEMCE). Koos A. Meritsa, M. Karelsoni ja T. Tensoniga uuritakse erinevate ühendite bioaktiivsust ja nende võimalikke rakendusi biomeditsiinis.
Tähtsamad tulemused
Välja on töötatud elektronirikaste areenide elektrokeemiline hüdroksüülimise transformatsioon, mis viiakse läbi pideva voolu tingimustes. Meetod võimaldab saada tundlikke tooteid vaid 1,25-minutilise viibimisega. Väärtuslikud hüdroksüülitud areenid saadi hea saagisega ilma kahjulike stöhhiomeetriliste oksüdeerijate või metallkatalüüsaatorite kasutamiseta, mis näitab selle esitatud elektrokeemilise protseduuri jätkusuutlikkust.Läbi on viidud 2-[(4-methylphenyl)thio]-2-cyclopenten-1-one asümmeetriline oksüdeerimine Ti(iPrO)4/(+)-DET/TBHP kompleksiga ning 2-[(4-methylphenyl)sulfinyl]- 2-cyclopenten-1-one sama Tikompleksiga. Mõlemal juhul saadi enantiorikastatud 2-(S)-[(4-methylphenyl)sulfinyl]-2-cyclopenten-1-one rahuldavaga saagisega ja piisava enantiomeerse puhtusega edasiseks enantiorikastamiseks ümberkristallimise teel. Saadud tulemused võimaldavad lihtsat juurdepääsu 9,11-sekosteroolide D-tsükli eelkäijale
Valminud on artikli käsikirjad: Lopušanskaja, E.; Paju, A.; Lopp, M. A Direct Alkylation of Resorcinols and Kõllo, M.; Rõuk, K.; Järving, I.; Pehk, T.; Lopp, M. Towards the total synthesis of 9,11-secosterol: linking A,B- and D-rings with Michael addition to sulfoxide and sulfone-activated cyclopentanones.
Seotud struktuuriüksus
Teadusgrupiga seotud publikatsioonid
- Kooli, A., Wesenberg, L., Beslać, M., Krech, A., Lopp, M., Noël, T., Ošeka, M. Electrochemical hydroxylation of electron-rich arenes in continuous flow // European journal of organic chemistry (2022) vol. 2022, 20, art. e202200540.
https://doi.org/10.1002/ejoc.202200011 - Kõllo, M., Rõuk, K., Lopp, M. Synthesis of 2-(S)-[(4-methylphenyl)sulfinyl]-2-cyclo penten-1-one, a D-ring precursor of 9,11-secosterols // Proceedings of the Estonian Academy of Sciences (2022) vol. 71, 4, p. 307-313 : ill.
https://doi.org/10.3176/proc.2022.4.01 - Ivanova, L., Rausalu, K., Ošeka, M., Kananovich, D. G., Žusinaite, E., Tammiku-Taul, J., Lopp, M., Merits, A., Karelson, M. Novel analogues of the Chikungunya virus protease inhibitor: molecular design, synthesis, and biological evaluation // ACS omega (2021) vol. 6, 16, p. 10884–10896.
https://doi.org/10.1021/acsomega.1c00625 - Kananovich, D., Elek, G. Z., Lopp, M., Borovkov, V. Aerobic oxidations in asymmetric synthesis : catalytic strategies and recent developments // Frontiers in chemistry (2021) vol. 9, art. 614944.
https://doi.org/10.3389/fchem.2021.614944 - Kooli, A., Shalima, T., Lopušanskaja, E., Paju, A., Lopp, M. Selective C-alkylation of substituted naphthols under non-aqueous conditions // Tetrahedron (2021) vol. 95, art. 132278, 8 p. : ill.
https://doi.org/10.1016/j.tet.2021.132278 - Kõllo, M., Kasari, M., Kasari, V., Pehk, T., Järving, I., Lopp, M., Jõers, A., Kanger, T. Designed whole-cell-catalysis-assisted synthesis of 9,11-secosterols // Beilstein journal of organic chemistry (2021) vol. 17, p. 581–588.
https://doi.org/10.3762/bjoc.17.52 - Puthiya Veetil, S.K., Rebane, K., Yörük, C.R., Lopp, M., Trikkel, A., Hitch, M. Aqueous mineral carbonation of oil shale mine waste (limestone) : a feasibility study to develop a CO2 capture sorbent // Energy (2021) vol. 221, art. 119895.
https://doi.org/10.1016/j.energy.2021.119895 - Kaldas, K., Niidu, A., Preegel, G., Uustalu, J. M., Muldma, K., Lopp, M. Aspects of kerogen oxidative dissolution in subcritical water using oxygen from air // Oil shale (2021) 3, p. 199-214 : ill.
https://doi.org/10.3176/oil.2021.3.02 - Lopušanskaja, E., Kooli, A., Paju, A., Järving, I., Lopp, M. Towards ortho-selective electrophilic substitution/addition to phenolates in anhydrous solvents // Tetrahedron (2021) vol. 83, 12, art. 131935, 9 p.
https://doi.org/10.1016/j.tet.2021.131935 - Niidu, A., Grénman, H., Muldma, K., Kaldas, K., Mikli, V., Lopp, M. Behavior of Estonian oil shale in acidic oxidative conditions // Frontiers in Chemical Engineering (2022) vol. 4, art. 590115.
https://doi.org/10.3389/fceng.2022.590115 - Kananovich, D. G., Lopp, M. Chirogenesis in asymmetric synthesis and catalysis // Chirogenesis in Chemical Science. Singapore : World Scientific Publishing, 2023. p. 169-240.
https://doi.org/10.1142/9789811259227_0004 - Zubrytski, D. M., Elek, G. Z., Lopp, M., Kananovich, D. G. Generation of mixed anhydrides via oxidative fragmentation of tertiary cyclopropanols with phenyliodine(III) dicarboxylates // Molecules (2020) vol. 26, 1, art. 140.
https://doi.org/10.3390/molecules26010140 - Lopušanskaja, E., Paju, A., Järving, I., Lopp, M. Synthesis of cyclic 3-aryl-substituted 1,2-dicarbonyl compounds via Suzuki cross-coupling reactions // Synthesis (2018) vol. 50, 9, p. 1883-1890 : ill.
https://doi.org/10.1055/s-0036-1591543 - Maljutenko, K., Borovkov, V., Kananovich, D., Järving, I., Lopp, M. Aerobic cascade oxidation of substituted cyclopentane-1,2-diones using metalloporphyrin catalysts // Tetrahedron (2018) vol. 74, 6, p. 661−664 : ill.
https://doi.org/10.1016/j.tet.2017.12.009 - Kaldas, K., Preegel, G., Muldma, K., Lopp, M. Reactivity of aliphatic dicarboxylic acids in wet air oxidation conditions // Industrial & engineering chemistry research (2019) vol. 58, 25, p. 10855–10863 : ill.
https://doi.org/10.1021/acs.iecr.9b01643 - Kaldas, K., Preegel, G., Muldma, K., Lopp, M. Wet air oxidation of oil shales: kerogen dissolution and dicarboxylic acid formation // ACS omega (2020) vol. 5, 35, p. 22021−22030.
https://doi.org/10.1021/acsomega.0c01466 - Elek, G.Z., Koppel, K., Zubrytski, D., Konrad, N., Järving, I., Lopp, M., Kananovich, D. Divergent access to histone deacetylase inhibitory cyclopeptides via a late-stage cyclopropane ring Cleavage strategy. Short synthesis of Chlamydocin // Organic letters (2019) vol. 21, 20, p. 8473-8478 : ill.
https://doi.org/10.1021/acs.orglett.9b03305 - Aid, T., Koel, M., Lopp, M., Vaher, M. Metal-catalyzed degradation of cellulose in ionic liquid media // Inorganics (2018) vol. 6, 3, art. 78, 11 p. : ill.
https://doi.org/10.3390/inorganics6030078 - Mets, B., Kaldas, K., Uustalu, J. M., Lopp, M. The Lille-Blokker model – an excellent tool to describe the structure of kukersite // Oil shale (2023) vol. 40, 3, p. 234−243.
https://doi.org/10.3176/oil.2023.3.04 - Mets, B., Lopp, M., Uustalu, J.M., Muldma, K., Niidu, A., Kaldas, K. A two-step model for assessing the potential of shale-derived chemicals by oxidation of kukersite // Oil shale (2023) vol. 40, 4, p. 344-362.
https://doi.org/10.3176/oil.2023.4.04