Organic Chemistry, Catalysis, Physical and Theoretical Chemistry, Colloid and Surface Chemistry
5
Scopus Publications
Scopus Publications
A data-driven and quantum chemistry-anchored framework for modeling and classifying carbon–lithium bonding in organolithium aggregates Valery A. Verkhov, Stepan A. Meshalkin, Alexander S. Antonov, Elena Yu. Tupikina Journal of Chemical Physics, 2025 We present a quantum chemistry-based, data-driven framework for the automated classification of carbon–lithium bonding motifs in archetypal organolithium aggregates. Starting from ab initio potential energy surfaces-guided sampling, we constructed a chemically complete dataset of 81 optimized gas-phase aggregates of methyllithium, t-butyllithium, and phenyllithium (600 C–Li bonds in total) spanning all relevant nuclearities and bonding modes. Twenty geometric, electronic, and topological descriptors obtained from quantum theory of atoms in molecules and Electron Localization Function (ELF) analyses were evaluated via correlation clustering, yielding a minimal, non-redundant, chemically meaningful set dominated by the ELF basin electron population and key bond-path metrics. This reduced descriptor set was used to train two complementary supervised models—a multi-task fully connected neural network and a bootstrap-aggregated decision tree—achieving accuracies of 84% (nucleophile type), 89% (aggregation state), and 84% (bond type) on validation data. Both methods consistently identified ELF-derived descriptors as the most discriminative, enabling physically grounded separation of bonding regimes (2c–2e, multi-center, non-classical, π–Li) and providing an interpretable, transferable platform for high-throughput bonding analysis in organometallic chemistry.
Flipping the Metalation of 4-Dimethylaminopyridine: Steric Repulsion versus London Dispersion Attraction Valery A. Verkhov, Alexandra N. Gubanova, Daria I. Tonkoglazova, Elena Yu. Tupikina, Alexander S. Antonov Chemistry A European Journal, 2025 Non‐covalent interactions, including the coordination of an organolithium reagent by a directing group and the steric hindrance from substituents, play a crucial role in determining the selectivity of metalation reactions. Here, we demonstrate the effective utilization of steric interactions for flipping the lithiation of 4‐dimethylaminopyridine (DMAP). Introduction of a Me3Si substituent to the position 1 of DMAP or simple complexation with t‐BuLi allows selective C3‐lithiation, due to the steric hindrance of a C2−H bond by the bulky moiety at the pyridine nitrogen. This simple approach creates a convenient way to achieve the selective C3‐functionalization of DMAP. In contrast, the utilization of an even bulkier i‐Pr3Si substituent leads to exclusive C2‐functionalization due to the dispersion interactions with organometallic bases. For the first time, it is demonstrated that the i‐Pr3Si moiety can serve as a directing group, providing a new type of directed ortho‐metalation effect.
Organoboron Derivatives of 1,8-Bis(dimethylamino)naphthalene: Synthesis, Structure, Stability, and Reactivity Victor G. Bardakov, Artyom A. Yakubenko, Valeriy A. Verkhov, Alexander S. Antonov Organometallics, 2022 A series of ortho-, meta-, and para-boronic acids and their pinacol esters of 1,8-bis(dimethylamino)naphthalene (DMAN), including the very first naphtho[1,8-cd][1,2,6]oxadiborinine-based proton sponge, were synthesized with moderate to good yields. The ease of deborylation of sterically hindered ortho-boronic acids of DMAN was demonstrated. DMAN-based 3,6-diboronic acid and its pinacol ester─valuable precursors for meta-derivatives of the naphthalene proton sponge─were prepared and utilized for the synthesis of 3,6-diiodo-DMAN. Obtained acids and esters were tested for common palladium and copper catalyzed couplings.
