Search Results (3)

The results of my research in the fields of theoretical studies and computer modeling of supramolecular chemical systems were presented. The main attention was focused on theoretical studies in the following topics: cycloaddition and nucleophilic addition reactions involving substrates with multiple CC and CN bonds, their mechanisms, driving forces, kinetics and thermodynamics; the consideration of the catalysis of hydrocarbons oxidation processes and their conversion to alcohols, ethers, aldehydes, ketones and carboxylic acids; investigations of various unusual types of non-covalent interactions (from quite trivial hydrogen bonds to more exotic σ-hole, π-hole and metallophilic interactions) in organic, organometallic and coordination compounds. Some fundamental issues of supramolecular chemical systems were also discussed (e.g., structure and properties of chemical compounds and their supramolecular associates; conformational transitions and rotation barriers of functional groups; nature of chemical bonds; orbital and charge factors; photophysical properties). Full article

A study on the reactivity of 3-amino α,β-unsaturated γ-lactam derivatives obtained from a multicomponent reaction is presented. Key features of the substrates are the presence of an endocyclic α,β-unsaturated amide moiety and an enamine functionality. Following different synthetic protocols, the functionalization at three different positions of the lactam core is achieved. In the presence of a soft base, under thermodynamic conditions, the functionalization at C-4 takes place where the substrates behave as enamines, while the use of a strong base, under kinetic conditions, leads to the formation of C-5-functionalized γ-lactams, in the presence of ethyl glyoxalate, through a highly diastereoselective vinylogous aldol reaction. Moreover, the nucleophilic addition of organometallic species allows the functionalization at C-3, through the imine tautomer, affording γ-lactams bearing tetrasubstituted stereocenters, where the substrates act as imine electrophiles. Taking into account the advantage of the presence of a chiral stereocenter in C-5 substituted γ-lactams, further diastereoselective transformations are also explored, leading to novel bicyclic substrates holding a fused γ and δ-lactam skeleton. Remarkably, an example of a highly stereoselective formal [3+3] cycloaddition reaction of chiral γ-lactam substrates is reported for the synthesis of 1,4-dihidropyridines, where a non-covalent attractive interaction of a carbonyl group with an electron-deficient arene seems to drive the stereoselectivity of the reaction to the exclusive formation of the cis isomer. In order to unambiguously determine the substitution pattern resulting from the diverse reactions, an extensive characterization of the substrates is detailed through 2D NMR and/or X-ray experiments. Likewise, applications of the substrates as antiproliferative agents against lung and ovarian cancer cells are also described. Full article