Laboratory of Electrochemical Synthesis

Development of an effective strategy for the directed synthesis of practically significant chemical compounds based on direct activation and subsequent functionalization of the C(sp2)-H bond of aromatic and heteroaromatic compounds (with the formation of new C-P, C-N, C-C bonds) under mild electrocatalytic conditions, by establishing key intermediates and their properties, mechanisms of catalytic reactions, their regularities by a complex of modern methods, including electrochemistry and EPR methods. The strategy being developed is based on controlling the selectivity of the transformation by the electrolysis potential, which ensures the oxidation of a specific participant in the process (either a metal, a ligand, a metallocycle with an M-C bond, or a combination partner) lying on the reaction path and determining the effectiveness of the entire catalytic cycle as a whole. It is supposed to solve the problem of involving difficult-to-react or previously unexplored partners in the target combination. An important problem and complexity of such metal-catalyzed C-H transformations in classical organic chemistry is a strong dependence on reaction conditions (choice of oxidant, ligands and combination partners), unproven mechanisms, unpredictable ligand-metal cooperation with possible ligand- and/or metal-centered electron transfers, often undesirable generation of substrate-ligand cation radicals Electrochemical methods, as planned, should make it possible to accurately assess the redox activity of each precursor and key identified intermediate of the catalytic cycle, to understand how the oxidative potential of participants in a multielectronic catalytic process changes and how selectivity can be controlled by changing this potential or adding the necessary reagents. Special attention is paid to the establishment of the structure and reactivity of metallocyclic intermediates (transition metal: Co, Cu, Pd, etc.) in ligand-directed C-H functionalization, factors stabilizing or contributing to their formation and, conversely, favoring reductive elimination. Various guiding groups are analyzed as an effective tool for the functionalization of the C –H bond, metallocyclic complexes (primarily Co, Pd, etc.) are synthesized on their basis and their reactivity and catalytic and redox activity, and, most importantly, the factors determining them, are established.