A selective synthesis of unsymmetrically functionalized disiloxanes via the subsequent hydrosilylation of internal alkynes in the first step, and alkynes (terminal or internal) or 1,3-diynes in the ...second, with 1,1,3,3-tetramethyldisiloxane (1) is presented for the first time. Using developed approaches performed in a stepwise or one-pot manner a new family of disubstituted disiloxanes was obtained which had previously been inaccessible by other synthetic methods. Moreover, symmetrically functionalized disiloxanes were obtained by direct hydrosilylation of 2 equivalents of terminal or internal alkynes with 1, showing the unique versatility of the hydrosilylation process. Three examples of symmetric disiloxanes were characterized by single crystal X-ray diffraction for the first time. As a result, a wide group of new compounds which can find potential applications as building blocks or coupling agents was obtained and characterized.
A readily available stereodynamic and the electronic circular dichroism (ECD)-silent 2,5-di(1-naphthyl)-terephthalaldehyde-based probe has been applied for chirality sensing of primary amines. The ...chiral amine (the inductor) forces a change in the structure of the chromophore system through the point-to-axial chirality transmission mechanism. As a result, efficient induction of optical activity in the chromophoric system is observed. The butterflylike structure of the probe, with the terminal aryl groups acting as changeable “wings”, allowed for the generation of exciton Cotton effects in the region of 1Bb electronic transition in the naphthalene chromophores. The sign of the exciton couplets observed for inductor–reporter systems might be correlated with an absolute configuration of the inductor, whereas the linear relationship between amplitudes of the specific Cotton effect and enantiomeric excess of the parent amine gives potentiality for quantitative chirality sensing. Despite the structural simplicity, the probe turned out to be unprecedentedly highly sensitive to even subtle differences in the inductor structure (i.e., O vs CH2).
The molecular recognition process and the ability to form multicomponent supramolecular systems have been investigated for the amide of triphenylacetic acid and l-tyrosine (
...-triphenylacetyl-l-tyrosine, TrCOTyr). The presence of several supramolecular synthons within the same amide molecule allows the formation of various multicomponent crystals, where TrCOTyr serves as a chiral host. Isostructural crystals of solvates with methanol and ethanol and a series of binary crystalline molecular complexes with selected organic diamines (1,5-naphthyridine, quinoxaline, 4,4'-bipyridyl, and DABCO) were obtained. The structures of the crystals were planned based on non-covalent interactions (O-H···N or N-H
···O
hydrogen bonds) present in a basic structural motif, which is a heterotrimeric building block consisting of two molecules of the host and one molecule of the guest. The complex of TrCOTyr with DABCO is an exception. The anionic dimers built off the TrCOTyr molecules form a supramolecular gutter, with trityl groups located on the edge and filled by DABCO cationic dimers. Whereas most of the racemic mixtures crystallize as racemic crystals or as conglomerates, the additional tests carried out for racemic
-triphenylacetyl-tyrosine (
-TrCOTyr) showed that the compound crystallizes as a solid solution of enantiomers.
The cascade process of a dynamic chirality transmission from the permanent chirality center to the stereodynamic triphenylmethyl group has been studied for series of optically active trityl ...derivatives. The structural analysis, carried out with the use of complementary methods, enabled us to determine the mechanism of chirality transfer. The process of chirality transmission involves a set of weak but complementary electrostatic interactions. The induction of helicity in a trityl propeller is revealed by rising non-zero cotton effects in the area of trityl UV-absorption. The presence of an additional stereogenic center in close proximity to the trityl-containing stereogenic center significantly affects the sign and, to a lesser extent, magnitude of the respective cotton effects. Despite the bulkiness of the trityl, in the crystalline phase, the molecules under study strictly fill the space. In the crystal, molecules form aggregates stabilized by OH•••O hydrogen bonds. However, the presence of two trityl groups precludes formation of OH•••O hydrogen bonding. Additionally, the trityl group seems to be responsible for the formation of the solid solutions by e.g., racemates of
- and
-2-tritylcyclohexanol. Therefore, the trityl group acts as a supramolecular protective group, which in turn can be used in the crystal engineering.
The electronic circular dichroism (CD)-silent 2,5-bis(biphen-2-yl)terephthalaldehyde has been used as a sensor (reporter) of chirality for primary amines. The through-space inductor–reporter ...interactions force a change in the chromophore conformation toward one of the diastereomeric forms. The structure of the reporter, with the terminal flipping biphenyl groups, led to generating Cotton effects in both lower- and higher-energy regions of the ECD spectrum. The induction of an optical activity in the chromophore was due to the cascade point-to-axial chirality transmission mechanism. The reporter system turned out to be sensitive to the subtle differences in the inductor structure. Despite the size of the chiral substituent, the molecular structure of the inductor–reporter systems in the solid-state showed many similarities. The most important one was the tendency of the core part of the molecules to adapt pseudocentrosymmetric conformation. Supported by a weak dispersion and Van der Waals interactions, the face-to-face and edge-to-face interactions between the π-electron systems present in the molecule were found to be responsible for the molecular arrangement in the crystal.
Palladacyclic architectures have been shown as versatile motifs in cross-coupling reactions. NHC-ligated palladacycles possessing unique electronic and steric properties have helped to stabilize the ...catalytically active species and provide additional control over reaction selectivity. Here, we report on a synthetic protocol leading to palladacycle complexes using a mild base and an environmentally desirable solvent, with a focus on complexes bearing backbone-substituted N-heterocyclic carbene ligands. The readily accessible complexes exhibit high catalytic activity in the Buchwald–Hartwig amination. This is achieved using low catalyst loading and mild reaction conditions in a green solvent.
A series of binary oxide systems with Ca/Si molar ratios of 0.05, 0.1, 0.25, 0.5 and 1.0 have been synthesized by the sol-gel technique from tetraethyl orthosilicate (TEOS) and metallic calcium ...powder. Upon calcination, a side effect of wollastonite formation as a result of the reaction between the components of the material has been observed in the two calcium-richest systems. The increase in calcium content produces an effect of porosity promotion. At high calcium contents, the homogeneity of the systems is limited by the ability of silica to disperse the calcium component. The properties of these systems are determined by the silica surface coverage with a large amount of the scattered CaCO3 fine microcrystallites (calcite), resulting from the phase segregation. The gels were characterized by X-ray powder diffraction, low temperature nitrogen adsorption, transmission and scanning electron microscopy (TEM, SEM and SEM/EDS), thermogravimetric analysis (TGA), and FT-IR spectra, to describe the parameters important from the point of view of their application as a support for metal-based catalysts.
Chirality transfer from circular dichroism (CD)-silent secondary alcohol (inductor) to the stereodynamic bichromophoric di(1-naphthyl)methane probe (reporter) led to the generation of intense, ...induced exciton-type Cotton effects (CEs) in the ultraviolet–visible absorption region. The di(1-naphthyl)methane probe exhibits extraordinarily high sensitivity to even small structural variations of the alcohol skeleton, that is, the probe is able to distinguish between an oxygen atom and a methylene group in a 3-hydroxytetrahydrofurane skeleton. Signs and amplitudes of the exciton couplets of 1Bb electronic transition might be correlated with the type of stereo-differentiating parts of the molecule flanking the stereogenic center, however, not with the absolute configuration. The origin of the induced CEs was established by means of experimental and theoretical methods. As a result, a mechanism of chirality transfer from the permanent stereogenic center to the bichromophore is proposed.
The structure of N‐triphenylacetyl‐l‐tyrosine (C29H25NO4, l‐TrCOTyr) is characterized by the presence of both donors and acceptors of classical hydrogen bonds. At the same time, the molecule contains ...a sterically demanding and hydrophobic trityl group capable of participating in π‐electron interactions. Due to its large volume, the trityl group may favour the formation of structural voids in the crystals, which can be filled with guest molecules. In this article, we present the crystal structures of a series of N‐triphenylacetyl‐l‐tyrosine solvates with chloroform, namely, l‐TrCOTyr·CHCl3 (I) and l‐TrCOTyr·1.5CHCl3 (III), and dichloromethane, namely, l‐TrCOTyr·CH2Cl2 (II) and l‐TrCOTyr·0.1CH2Cl2 (IV). To complement the topic, we also decided to use the racemic amide N‐triphenylacetyl‐dl‐tyrosine (rac‐TrCOTyr) and recrystallized it from a mixture of chloroform and dichloromethane. As a result, rac‐TrCOTyr·1.5CHCl3 (V) was obtained. In the crystal structures, the amide molecules interact with each other via O—H…O hydrogen bonds. Noticeably, the amide N—H group does not participate in the formation of intermolecular hydrogen bonds. Channels are formed between the TrCOTyr molecules and these are filled with solvent molecules. Additionally, in the crystals of III and V, there are structural voids that are occupied by chloroform molecules. Structure analysis has shown that solvates I and II are isostructural. Upon loss of solvent, the solvates transform into the solvent‐free form of TrCOTyr, as confirmed by thermogravimetric analysis, differential scanning calorimetry and powder X‐ray diffraction.
A series of new N‐triphenylacetyltyrosine solvates was obtained by recrystallization and they were structurally characterized. The channels in the crystal structures are filled with solvent molecules, the positions of which are stabilized by weak interactions. After removing the solvent molecules, the solvate crystals transform into the solvent‐free forms of the amide.
We have proven the usability and versatility of chiral triphenylacetic acid esters, compounds of high structural diversity, as chirality-sensing stereodynamic probes and as molecular tectons in ...crystal engineering. The low energy barrier to stereoisomer interconversion has been exploited to sense the chirality of an alkyl substituent in the esters. The structural information are cascaded from the permanently chiral alcohol (inducer) to the stereodynamic chromophoric probe through cooperative interactions. The ECD spectra of triphenylacetic acid esters are highly sensitive to very small structural differences in the inducer core. The tendencies to maximize the C–H···O hydrogen bonds, van der Waals interactions, and London dispersion forces determine the way of packing molecules in the crystal lattice. The phenyl embraces of trityl groups allowed, to some extent, the control of molecular organization in the crystal. However, the spectrum of possible molecular arrangements is very broad and depends on the type of substituent, the optical purity of the sample, and the presence of a second trityl group in the proximity. Racemates crystallize as the solid solution of enantiomers, where the trityl group acts as a protecting group for the stereogenic center. Therefore, the absolute configuration of the inducer is irrelevant to the packing mode of molecules in the crystal.
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