The review presents the most relevant developments in the field of dynamic supramolecular stereochemistry, the introduction of its basic concepts: supramolecular chiral center, supramolecular configuration, crystallization-induced stereochemical transformation, supramolecular diastereomeric forms. Using a specially selected collection of crystal structures of chiral compounds containing various groupings as a prostereogenic ensemble: a sulfonyl group, a methylene group, diastereotopic lone pairs and sides of a carbonyl group shows the possibility of forming supramolecular diastereomers due to the differentiation of diastereotopic elements. For the series of compounds, an understanding has been achieved of which diastereomeric form of the supramolecular level (or both at the same time) is required for the implementation of a particular supramolecular synthon or motif (dimer, tetramer, homo- or heterochiral chain). Examples of successful development of a scheme for directed "supramolecular synthesis" of substances in a specific supramolecular configuration are presented. The proposed approach is highly relevant because traditional crystallographic analysis often overlooks the stereochemical nonequivalence of atoms in prostereogenic groups. This review shows that it is precisely this inconsistency that underlies many phenomena that were previously explained simply by "conformational mobility" or randomness: Z' > 1, pseudosymmetry, and the appearance of two independent molecules with different geometries.

Within the framework of the developing field of supramolecular dynamic stereochemistry, the ability of a steviol derivative to form two stereochemically different types of homochiral dimers in crystals, namely non-symmetrical and pseudo-symmetrical, has been studied. The first type of dimer is formed by molecules of two different supramolecular diastereomers and the second type is formed by two identical ones. The formation of two different supramolecular diastereomeric forms based on the steviol molecule occurs at the stage of formation of hydrogen bonds involving stereochemically identical or different LPs of the hydroxyl oxygen atom. The analysis of the electron density Laplacian function, performed on the optimized geometry of dimers of both types, made it possible to carry out an evidence-based correlation, as well as to visualize the participation of one or another LP in a specific intradimeric hydrogen bond. Controlled conditions for obtaining phases containing dimers of a particular configuration as building blocks and the transition conditions between them were revealed.

The rational design of crystalline materials capable of chiral discrimination remains a central challenge in crystal engineering. Here, we report a crystal engineering study of a novel family of 2-arylmethylidene thiazolo[3,2-a] pyrimidine derivatives bearing an ortho-methoxyphenyl substituent. Single-crystal X-ray analysis of twelve compounds 5-16 revealed a consistent intramolecular n -> it* interaction between the methoxy oxygen and the pyrimidyl nitrogen atoms, which acts as a conformational lock. This preorganization, combined with the electronic activation of the nitrogen acceptor site, is shown to be a critical factor in steering supramolecular assembly. While derivatives with ester groups predominantly form racemic dimers or heterochiral chains, the introduction of strong electron-withdrawing nitro groups shifts the balance towards the formation of homochiral chains and layers stabilized by strengthened O-H center dot center dot center dot N hydrogen bonds and directional it-stacking. This work demonstrates that the ortho-methoxy group serves as a powerful intramolecular tool for tuning chiral discrimination in the solid state, providing a rational strategy for the design of homochiral assemblies from achiral building blocks.

The reactivity of mucochloric acid and its 5-substituted derivatives towards 2,2'-oxydiethanethiol was studied. A specific feature of the reaction of mucochloric acid with 2,2'-oxydiethanethiol carried out in the presence of triethylamine was revealed. Compared to previously studied reactions with aliphatic dithiols, minor products of the lactone ring degradation, possessing a propenal fragment, were also isolated in this reaction, along with a bis-thioether of the 2(5H)-furanone series. A series of novel bis-thioethers and thiols containing an unsaturated γ-lactone ring and a dithiol fragment were synthesized and characterized.

In a series of three chiral thioureas bearing a tetrahydronaphthyl fragment, none of the homochiral samples forms "true chiral" hydrogen-bonded motifs in the crystal. In all three cases, the addition of a second independent molecule to the cell is observed. In one case, a pseudosymmetric dimer was found in the crystal, and in the other two cases, a chain motif with alternation of independent molecules was found. The conformational transformations of the thiourea fragment are considered.

In this study, we have shown for the first time that the introduction of a single alkylamide substituent into the macrocyclic platform of pillar[5]arene opens up the possibility to control the supramolecular properties of this macrocyclic platform. The ability of the synthesized pillar[5]arenes to form supramolecular pseudorotaxane associates both in solutions and in the crystalline state was studied by a complex of physical methods. Linear secondary amide fragments such as N,N-diethylethane-1,2-diamide, N,N-dimethylpropane-1,3-diamide, or N-aminoethylmorpholide in the structure of pillar[5]arene promote the formation of self-inclusion complexes both in solution and crystalline states. Whereas tertiary amides such as pyrrolidide or morpholide moieties favor the formation of supramolecular polymers both in solution and in crystalline states. The obtained results show the prospects for the use of amide fragments in the structures of pillar[n]arenes as customization units for controlling supramolecular self-assembly.

Синтезированы новые оптически активные тиоэфиры и сульфоны на основе 2(5Н)-фуранона, 4-аминотиофенола и двух монотерпеновых спиртов – l-ментола и l-борнеола. Методом рентгеноструктурного анализа исследована кристаллическая структура двух оптически активных сульфонильных производных фуранонового ряда. В обоих кристаллах вещество представлено независимыми молекулами А и В, имеющими радикальные различия в конформациях и системе водородных связей. Показана продуктивность подхода детального рассмотрения всех стереохимических особенностей молекулы в кристалле по данным РСА с привлечением анализа поверхностей Хиршфельда.

Methods for the synthesis of novel heterocyclic compounds bearing an unsaturated γ-lactone ring and an (S)-naproxen moiety were developed. The O-acylation reactions of 3,4-dihalo-5-hydroxy-2(5H)-furanones with (S)-(+)-2-(6-methoxy-2-naphthyl)propionyl chloride in the presence of Et3N afforded optically active furanone derivatives bearing an (S)-naproxen moiety at the 5 position of the lactone ring. Optically active 4-arylsulfanyl derivatives of 2(5H)-furanone were obtained by the reaction of the isolated (R,S) stereoisomers of 3,4-dihalofuranones with aromatic thiols. A series of heterocycles were synthesized based on 5-alkoxy- and 5-haloahkoxy-2(5H)-furanones containing an (S)-naproxen moiety in the side chain of the hydroxyethylthio substituent on the carbon atom C(4) of the five-membered ring. The structures of three new heterocycles were determined by X-ray diffraction.

Получена новая кристаллическая Z' = 3 форма 15-ен-стевиола – 13-гидрокси-энт-каур-15-ен-19-овой кислоты. Методом рентгеноструктурного анализа обнаружен неизвестный ранее для соединений с каурановым скелетом ассоциат – гомохиральный циклический димер по типу «голова к голове, хвост к хвосту». Геометрия димера в кристалле и в газовой фазе по данными квантово-химических расчётов свидетельствует о напряжённости конструкции, проявляющейся в существенном отклонении от плоскости геометрии карбоксильного синтона. Проиллюстрировано отклонение неподеленных электронных пар карбонильных групп от связевых путей, показанное методом топологического анализа, дополненного анализом функции лапласиана электронной плотности.

Получены комплексы на основе двух структурно родственных карбоновых кислот на основе 3,5-биарил-2,3-дигидро-5H-тиазоло[3,2-a]пиримидинов и исследована их кристаллическая структура. Не являясь изоструктурными, комплексы сформированы принципиально одинаковым образом. Катион металла (магния или кальция) координирован по шести положениям молекулами растворителей, причём большее количество положений занято молекулами основного растворителя, а минорное(ые) – молекулой со-растворителя (вода в комплексе магния и этиленгликоль в комплексе кальция). Молекулы растворителей формируют собой первую координационную сферу катиона магния, составляя вместе с ним «катионное ядро». Наличие в первой координационной сфере металла «дефектных» позиций, занятых молекулами со-растворителя, является фактором, асимметризующим дальнейший рост комплекса. А именно, формирование второй координационной сферы анионами карбоновых кислот посредством первичных водородных связей O–H‧‧‧O типа происходит с участием двух лигандов одинаковой конфигурации со стороны, противоположной молекуле со-растворителя.

In order to reduce the impact of heavy metals on water systems, extraction methods are widely used. Thiamacrocycles are promising extractants for heavy metal cations due to their high affinity for these ions. Although a large number of non-functionalized thiamacrocyclic ligands have been synthesized, oxathiamacrocycles containing small rigid molecules have been less thoroughly studied. This work describes the synthesis and characterization of two novel 28- and 30-membered oxathiamacrocycles as [2+2] macrocyclization products obtained from the reaction of 5,5'-(ethane-1,2-diylbis(oxy))bis(3,4-dichlorofuran-2(5H)-one) with 2,2'-oxydiethanethiol and 1,2-phenylenedimethanethiol in the presence of Et3N. These multidonor sulfur-containing macrocycles represent interesting objects for studying their complexation and extraction properties.

In contrast to hypervalent iodine compounds, the chemistry of their sulfur analogues has been considerably less explored. Herein, we report the direct C-H bond thiolation of electron-rich heterocycles, arenes, and 1,3-dicarbonyls by dichlorosulfuranes under mild conditions. Mechanistic studies and density functional theory calculations suggest the radical chain mechanism of the disclosed transformation. The key to success is attributed to a strikingly low S-Cl bond dissociation energy, which enables the generation of radical species upon exposure to daylight.

Reactions between 4-(propargyloxy)benzaldehyde with anthracene-9-carbaldehyde oxime or pyrene-1-carbaldehyde oxime in the presence of chloramine T in ethanol lead to new isoxazole-containing derivatives of benzaldehyde. The subsequent acid-catalyzed condensation of these compounds with 2-methylresorcinol in chloroform/trifluoroacetic acid mixtures affords novel calix[4]resorcinols with anthaceneand pyrene-ended isoxazole-containing fragments as all–cis (rccc) and cis–trans–trans (rctt) diastereoisomers, their ratios being dependent on the CF3CO2H percentage in the medium. The crystal structures of pyrene-ended isoxazole-containing benzaldehyde and corresponding calix[4]resorcinol rctt isomer have been established by single crystal X-ray diffraction.

The coexistence of two fragments, a chiral isosteviol moiety and an achiral pyridinoyl-hydrazone moiety, in the molecules of pyridinoyl-hydrazone derivatives of isosteviol results in the realization of two distinct supramolecular motifs in their crystals, namely, a true homochiral motif and a pseudosymmetric homochiral motif.

The molecular structures and crystal packings of three new BODIPY compounds with a bromine atom in the alpha-, beta-, and gamma-position were analyzed. The asymmetrization of the central conjugated fragment was demonstrated for the first time, with its expression and localization determined by the position of the substituent relative to the borofluoride core of the molecule.

The design of biocompatible photosensitizers with an optimal combination of intense fluorescence and generation of singlet oxygen is a complex and urgent task. The article presents the results of synthesizing, analyzing the structure, and examining the chromophoric, fluorescent, and generation characteristics of new dimeric bis(beta-Br-BODIPY) (1), as well as the features of its encapsulation in ZIF-8 zeolite framework and solubilization by Pluronic (R) F127 micelles. The photophysical characteristics of brominated dimer 1 were analyzed in comparison with non-halogenated dimers bis(beta-H-BODIPY) (2), bis(beta-CH3-BODIPY) (3), as well as dibromo-substituted mononuclear analogue beta,beta-dibromo-BODIPY (4). Dye 1 exhibits efficient fluorescence (from 53 to 72%) and O-1(2) generation (from 19 to 42%) in solutions of nonpolar and weakly polar solvents. Dimerization leads to a high sensitivity of the fluorescence and generation characteristics of the halogenated dimer 1 to the solvent. The advantage of dimer 1 is a significantly lower tendency to aggregate compared to monomer 4. The conditions for the encapsulation of dye 1 in ZIF-8 nanoparticles and Pluronic (R) F127 micelles were determined and their structural and spectral characteristics were analyzed.

A series of optically active 5(S)-(l-bornyloxy)- and 5(S)-(l-menthyloxy)-2(5H)-furanones with an arylthio group at the C(4) position of the γ-lactone ring was synthesized and studied for its oxidation reactions with various reagents. Novel 2(5H)-furanone sulfoxides were obtained as mixtures of two diastereoisomers through the oxidation of arylthioethers with m-chloroperbenzoic acid (m-СРВА) or hydrogen peroxide in acetic acid. Individual stereoisomers of these sulfoxides were isolated using recrystallization and high-performance liquid chromatography (HPLC) and characterized by IR and NMR spectroscopy. The molecular structures of eight stereoisomerically pure compounds were confirmed by X-ray diffraction (XRD) analysis. The antibacterial activity of the novel sulfoxides against Staphylococcus aureus and Escherichia coli was assessed, with a number of compounds found to inhibit bacterial growth and biofilm formation in S. aureus.

The synthesis and characterization of previously unknown azides, iminophosphoranes and amines from commercially available mucochloric and mucobromic acids is reported. The reaction of 5-alkoxy-3,4-dihalo-2(5H)-furanones with sodium azide resulted in the regioselective formation of furanone 4-azidoderivatives. A series of novel iminophosphoranes was obtained from the reaction of corresponding azides with triphenylphosphine. Reduction of iminophosphoranes with stannous chloride dihydrate led to the heterocycles, possessing an amino group at the C4 carbon atom of the unsaturated γ-lactone ring.

In a series of three chiral thioureas with a 1-phenylethylamine fragment, none of the homochiral samples forms “true chiral” hydrogen-bonded motifs in the crystal, but forms dimers or chains with local symmetry from the interacting fragments, consistent with the racemic crystal pattern.

Allylboration of the 1,2,3-triazole and pyrazole aldehydes with triallylborane or 2,4-pentadienyl(dipropyl)borane under mild reaction conditions provides high yields of the corresponding novel homoallylic and dihomoallylic alcohols that can be used to modify the side chain in the triazole- or diazole-based molecules. Enantioselective allylboration of triazole aldehydes with (+)-B-allyldiisopinocampheylborane gave optically active R(+) homoallylic alcohols in good yields with 80–93