Degradation of dichloromethane by bispidine

Cui, Haozhe; Goddard, Richard; Pörschke, Klaus‐Richard

doi:10.1002/poc.2909

Cited by 20 publications

(38 citation statements)

References 74 publications

(134 reference statements)

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“…Selected geometrical features are listed in Table 1. The main geometrical parameters of the bispidine skeleton in all studied compounds are close to the values reported and discussed for numerous bispidines and their salts in [63] and references cited therein.…”

Section: Resultssupporting

confidence: 84%

“…The molecular structures of the diazaadamantane derivatives 1c and 1c+H 2 O are shown in Figures S15 and S17. The main geometrical features of the diazaadamantane scaffold in both compounds are close to those found for hydrochloride of the parent compound [63]. Notably, this is only the third known example of the cocrystallization of ketone and its hydrate [67,68].…”

Section: Resultssupporting

confidence: 53%

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

et al. 2019

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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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Section: Resultssupporting

confidence: 84%

Section: Resultssupporting

confidence: 53%

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

et al. 2019

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“…Both amide fragments (CH2)2N-C(=O)-C are planar within 0.03 Å. The main geometrical parameters of the bicyclic core in the studied compounds are close to the values reported and discussed for several bispidine derivatives in [38] and references cited therein. The heterocycles in 1i are close to an orthogonal disposition, and thus the observed conformation can be additionally stabilized by C-H…π interaction or S…π interaction.…”

Section: X-ray Studiessupporting

confidence: 84%

Bispidine Platform as a Tool for Studying Amide Configuration Stability

et al. 2022

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In this work, the solution conformations of seventeen 3,7-diacyl bispidines were studied by means of NMR spectroscopy including VT NMR experiments. The acyl groups included alkyl, alkenyl, aryl, hetaryl, and ferrocene moieties. The presence of syn/anti-isomers and their ratios were estimated, and some reasons explaining experimental facts were formulated. In particular, all aliphatic and heterocyclic units in the acylic R(CO) fragments led to an increased content of the syn-form in DMSO-d6 solutions. In contrast, only the anti-form was detected in DMSO-d6 and CDCl3 in the case when R = Ph, ferrocenyl, (R)-myrtenyl. In the case of a chiral compound derived from the natural terpene myrtene, a new dynamic process was found in addition to the expected inversion around the amide N-C(O) bond. Here, rotation around the CO-C=C bond in the acylic R fragment was detected, and its energy was estimated. For this compound, ΔG for amide N-C(O) inversion was found to be equal to 15.0 ± 0.2 kcal/mol, and for the rotation around the N(CO)–C2′ bond, it was equal to 15.6 ± 0.3 kcal/mol. NMR analysis of the chiral bispidine-based bis-amide was conducted for the first time. Two X-ray structures are reported. For the first time, the unique syn-form was found in the crystal of an acyclic bispidine-based bis-amide. Quantum chemical calculations revealed the unexpected mechanism for amide bond inversion. It was found that the reaction does not proceed as direct N-C(O) bond inversion in the double-chair (CC) conformation but rather requires the conformational transformation into the chair–boat (CB) form first. The amide bond inversion in the latter requires less energy than in the CC form.

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“…Selected geometrical features are listed in Table 1. Main geometrical parameters of the bispidine skeleton in all studied compounds are close to the values reported and discussed for numerous bispidines and their salts in [63] and references cited therein. In all presented cases both piperidine cycles of bicyclic skeleton adopt chair conformation with involuntarily shortened N…N separations (see Table 1).…”

Section: Introductionsupporting

confidence: 83%

“…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]. Notably, this is only the third known example of cocrystallization of ketone and its hydrate [67,68].…”

Section: Introductionmentioning

confidence: 98%

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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Degradation of dichloromethane by bispidine

Cited by 20 publications

References 74 publications

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

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

Bispidine Platform as a Tool for Studying Amide Configuration Stability

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

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Degradation of dichloromethane by bispidine

Cited by 20 publications

References 74 publications

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

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

Bispidine Platform as a Tool for Studying Amide Configuration Stability

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

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Product

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