<i>syn</i>-3-(4-Chlorobenzyl)-1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-ol

Kudryavtsev, Konstantin V.; Вацадзе, С. З.; Semashko, V. S.; Churakov, Andrei V.

doi:10.1107/s1600536812030310

Cited by 2 publications

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References 4 publications

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“…Search in the Cambridge Structural Database (CSD, ver. 5.39, Feb 2018) [65] It should be noted, that 3c is isostructural with its chlorine analogue LEFFIN (3b) [66]. hydrochloride of the parent compound [63].…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Organogels Based on N-Benzyl, N’-Acylbispidinols

Медведько

Dalinger

Nuriev

et al. 2018

Preprint

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The acylation of unsymmetrical N-benzylbispidinols in aromatic solvents without external base led to formation of supramolecular gels, which possess different thickness and stability depending on the substituents in para-positions of benzylic group and nature of acylating agent as well as on the nature of the solvent used. Structural features of the native gels as well as of their dried forms were studied by complementary techniques including FT IR-and ATR-spectroscopy, AFM, TEM, SEM, SAXS. Structures of the key crystalline compounds were established by X-ray diffraction. Analysis of obtained data allowed speculating on the crucial structural and condition factors that governed the gel formation. The most important factors were: (i) absence of base, either external or internal; (ii) presence of HCl; (iii) presence of carbonyl and hydroxyl groups to allow hydrogen bonding; (iv) presence of two (hetero)aromatic rings at both sides of the molecule. The hydrogen bonding involving amide carbonyl, hydroxyl at 9 th position and, very probably, ammonium N-H+ and Cl-anion appear to be responsible for the formation of infinite molecular chains required for the first step of gel formation. Subsequent lateral cooperation of molecular chains into fibers occured, presumably, due to the aromatic pi-pi-stacking interactions. sc-CO2 drying of the gels gave rise to aerogels morphology different from that of air dried samples. requires use of poly/multifunctional chelating agents that should form covalent bonds with various biomolecules/vectors possessing high specificity and selectivity towards certain targets [5], [8][9][10][11]. 3,7-Diazabicyclo[3.3.1]nonanes (hereafter called bispidines) are one of the privileged scaffolds in medicinal chemistry [12] due to the number of advantages, e.g. (i) high basicity and solubility in water and/or organic solvents [13,14]; (ii) ability to diverse functionalization including chiral derivatives [15][16][17][18][19][20]; (iii) deeply studied conformational features which allow application of some rigid conformation [21][22][23]. Our recent works have shown potential of using the bispidine scaffolds for design of inhibitors of serine proteases [24,25]. At the same time, bispidines are well-known ligands with high affinity to Cu(II) and some other bivalent metals [26][27][28][29]. Therefore, we focus on creating new potent ligands for 64 Cu PET based on number of unsymmetrically substituted bispidine-9-ols. During our work with ligands for serine proteases it was necessary to find a way to insert bulky groups into pockets of the active site [24,25]. The acylation reaction is one of the obvious ways to functionalize the secondary amine group in N-benzylbispidinols; the resulting N-benzyl, N'-acylbispidinols allow subsequent transformations like reduction of amide group or removal of the protecting benzylic group followed by diverse functionalization of the formed secondary amine. In the course of our work we have discovered an interesting phenomenon, namely, formation of gels during the acylatio...

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Section: Introductionmentioning

confidence: 99%

Supramolecular Organogels Based on N-Benzyl, N’-Acylbispidinols

Медведько

Dalinger

Nuriev

et al. 2018

Preprint

View full text Add to dashboard Cite

show abstract

Supramolecular Organogels Based on N-Benzyl, N′-Acylbispidinols

et al. 2019

View full text Add to dashboard Cite

The acylation of unsymmetrical N-benzylbispidinols in aromatic solvents without an external base led to the formation of supramolecular gels, which possess different thicknesses and degrees of stability depending on the substituents in para-positions of the benzylic group as well as on the nature of the acylating agent and of the solvent used. Structural features of the native gels as well as of their dried forms were studied by complementary techniques including Fourier-transform infrared (FTIR) and attenuated total reflection (ATR) spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and small-angle X-ray scattering and diffraction (SAXS). Structures of the key crystalline compounds were established by X-ray diffraction. An analysis of the obtained data allowed speculation on the crucial structural and condition factors that governed the gel formation. The most important factors were as follows: (i) absence of base, either external or internal; (ii) presence of HCl; (iii) presence of carbonyl and hydroxyl groups to allow hydrogen bonding; and (iv) presence of two (hetero)aromatic rings at both sides of the molecule. The hydrogen bonding involving amide carbonyl, hydroxyl at position 9, and, very probably, ammonium N-H+ and Cl− anion appears to be responsible for the formation of infinite molecular chains required for the first step of gel formation. Subsequent lateral cooperation of molecular chains into fibers occurred, presumably, due to the aromatic π−π-stacking interactions. Supercritical carbon dioxide drying of the organogels gave rise to aerogels with morphologies different from that of air-dried samples.

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syn-3-(4-Chlorobenzyl)-1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-ol

Cited by 2 publications

References 4 publications

Supramolecular Organogels Based on N-Benzyl, N’-Acylbispidinols

Supramolecular Organogels Based on N-Benzyl, N’-Acylbispidinols

Supramolecular Organogels Based on N-Benzyl, N′-Acylbispidinols

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syn-3-(4-Chlorobenzyl)-1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-ol

Cited by 2 publications

References 4 publications

Supramolecular Organogels Based on N-Benzyl, N&rsquo;-Acylbispidinols

Supramolecular Organogels Based on N-Benzyl, N&rsquo;-Acylbispidinols

Supramolecular Organogels Based on N-Benzyl, N′-Acylbispidinols

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Supramolecular Organogels Based on N-Benzyl, N’-Acylbispidinols

Supramolecular Organogels Based on N-Benzyl, N’-Acylbispidinols