- Sir William Ramsay Professor of Chemistry (Chemistry)
RA408 Level A4
Joseph Black Building
Glasgow G12 8QQ
Research in the Pavel Kocovsky group is focused on organic/organometallic synthesis and mechanisms, and includes asymmetric catalysis, quantum chemistry calculations, synthesis of biologically significant compounds and natural products, molecular probes to study biological systems, and immobilization of catalysts. We are mainly interested in the rational design of novel synthetic methods, in particular reactions catalysed or mediated by transition and non-transition metals (Pd, Mo, W, Ru, Ir, Ni, Zn, Cu, Tl, Hg, and Si). The primary goal in all our work is to devise and make use of synthetic routes that feature new chemistry. In all our efforts, we aim not just to reach our target molecules but to do so in an original and chemically interesting manner.
Because of their exceptional steric and electronic properties, transition metal complexes hold tremendous promise for effecting highly selective transformations of organic substrates, e.g., stereocontrolled reactions, sp2-sp2 coupling, and site-selective C-H activation. The central theme of our research is therefore the utilization of transition and non-transition metals to discover unprecedented reactivity and new transformations for use in organic chemistry. We also hope to learn more about the basic stereochemical and electronic control elements of metal-ligand interactions. Our work is characterized by initial mechanistic studies to uncover processes that can be nurtured into novel reactions. To date, we have also developed a number of chiral ligands, such as NOBIN, MAP, and PINDY.
In the past few years, we became interested in organocatalysis, i.e., reactions catalyzed by small, metal-free organic molecules, and have designed several new catalysts, in particular METHOX and QUINOX for the enantioselective allylation of aldehydes, and Kenamide and Sigamide for the enantioselective reduction of imines.
- “Mechanistic Dichotomy in the Asymmetric Allylation of Aldehydes with Allyltrichlorosilanes Catalyzed by Chiral Pyridine N-Oxides”. Malkov, A. V.; Stončius, S.; Bell, M.; Castelluzzo, F.; Ramírez-López, P.; Biedermannová, L.; Rulíšek, L.; Langer, V.; Kočovský, P. Chem. Eur. J. 2013, 19, 9167-9185.
- “Synthesis of Di- and Tri-Substituted Isoxazolidines and β-Amino-δ-Hydroxy Esters via a Stereoselective Palladium-Catalyzed Functionalization of Homoallylic Alcohols”. Malkov, A. V.; Barłóg, M.; Miller-Potucká, L.; Kabeshov, M. A.; Farrugia, L.; Kočovský, P. Chem. Eur J. 2012, 18, 6873-6884.
- “Asymmetric Reduction of Imines with Trichlorosilane Catalyzed by Amino Acid-Derived Formamides: Scope and Limitations”. Malkov, A. V.; Vranková, K.; Stončius, S.; Kočovský, P. J. Org. Chem. 2009, 74, 5839-5849.
- “On the Mechanism of Asymmetric Allylation of Aldehydes with Allyltrichlorosilanes Catalyzed by QUINOX, a Chiral Isoquinoline N-Oxide”. Malkov, A. V.; Bell, M.; Ramírez-López, P.; Biedermannová, L.; Rulíšek, L.; Dufková, L.; Kotora, M.; Zhu, F.; Kočovský, P. J. Am. Chem. Soc. 2008, 130, 5341.
- “Amino Alcohols as Organocatalysts in Asymmetric Cross-Aldol Reaction of Ketones: Application in the Synthesis of Convolutamydine A”. Malkov, A. V.; Kabeshov, M. A.; Bella, M.; Kysilka, O.; Malyshev, D. A.; Pluháčková, K.; Kočovský, P. Org. Lett. 2007, 9, 5473-5476.
- "Enantioselective Synthesis of 1,2-Diarylaziridines by the Organocatalytic Reductive Amination of alpha-Chloroketones". Malkov, A. V.; Stončius, S.; Kočovský, P. Angew. Chem. Int. Ed. 2007, 46, 3722-3724.
- "Asymmetric Allylic Substitution Catalyzed by C1-Symmetrical Complexes of Molybdenum: Structural Requirements of the Ligand and Stereochemical Course of Reaction". Malkov, A. V.; Starý, I.; Gouriou, L.; Lloyd-Jones, G. C.; Langer, V.; Spoor, P.; Vinader, V.; Kočovský, P. Chem. Eur. J. 2006, 12, 6910-6929.
- "Remote Chiral Induction in the Organocatalytic Hydrosilylation of Aromatic Ketones and Ketimines". Malkov, A. V.; Stewart Liddon, A. J. P.; Ramírez-López, P.; Bendová, L.; Haigh, D.; Kočovský, P. Angew. Chem. Int. Ed. 2006, 45, 1432-1435.