What is responsible for conformational diversity in single-crystal tetraoxazaspiroalkanes? X-Ray, DFT, and AIM approaches

Tulyabaev, Arthur R.; Bikmukhametov, Kamil Sh.; Mescheryakova, Ekaterina S.; Makhmudiyarova, N. N.; Rakhimov, Rustem Sh.; Халилов, Л. М.

doi:10.1039/c8ce00481a

Cited by 5 publications

(9 citation statements)

References 47 publications

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“…One local minimum on the potential energy surface is attributable to a boat-chair conformation, whereas the second is assigned to a twist-boatchair conformation. It should be noted that we previously identified these conformations for other tetraoxazocane derivatives (Tulyabaev et al, 2018). Twist-boat-chair is the least attainable conformation for the tetraoxazocane ring bound to menthone and oxazole substituents, whereas the energy barrier between the boat-chair and chair-chair conformers is small at 1.62 kcal mol À1 (Table 4).…”

Section: Conformational Analysismentioning

confidence: 84%

“…The tetraoxazocane ring adopts a boat-chair conformation, in contrast to the menthone tetraoxazocanes (chair-chair) and adamantane tetraoxazocanes (twist-boat-chair) (Tulyabaev et al, 2018). Despite the fact that the tetraoxazocane ring is apparently symmetrical, a detailed analysis of its bond lengths showed that they are non-equivalent due to the C6 chiral centre.…”

Section: Molecular Structurementioning

confidence: 93%

“…7). In our previous work (Tulyabaev et al, 2018), we showed that intramolecular interactions can determine the conformational preference of a wide range of tetraoxazocanes. In the case of compound (I), we may also assume that these intramolecular bonds probably lead to the boat-chair conformation of the tetraoxazocane ring.…”

Section: Tablementioning

confidence: 95%

“…The molecular and crystal structures of a new tetraoxazocane derivative, namely (2S,5R)-2-isopropyl-5-methyl-7-(5-methylisoxazol-3-yl)cyclohexanespiro-3 0 -(1,2,4,5,7-tetraoxazocane), (I), with potential antimalarial and antitumour activities is studied in this work. We earlier studied the mol-ecular and crystal structures of similar menthone and adamantane tetraoxazocanes containing halogenophenyl substituents at the N atom, in which the tetraoxazocane fragment possessed chair-chair and twist-boat-chair conformations, respectively (Tulyabaev et al, 2018). Stereoelectronic effects in the eight-membered heterocycle on the N-C-O and O-C-O fragments were also observed.…”

Section: Introductionmentioning

confidence: 99%

“…In this work, we compare compound (I) with (II) [systematic name: 7-(3-chlorophenyl)-2-isopropyl-5-methylcyclohexanespiro-3 0 -(1,2,4,5,7-tetraoxazocane)] described previously (Tulyabaev et al, 2018) (see Scheme 1) and show how the oxazole group influences the molecular and crystal structures.…”

Section: Introductionmentioning

confidence: 99%

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How the oxazole fragment influences the conformation of the tetraoxazocane ring in a cyclohexanespiro-3′-(1,2,4,5,7-tetraoxazocane): single-crystal X-ray and theoretical study

et al. 2019

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Single crystals of (2S,5R)‐2‐isopropyl‐5‐methyl‐7‐(5‐methylisoxazol‐3‐yl)cyclohexanespiro‐3′‐(1,2,4,5,7‐tetraoxazocane), C16H26N2O5, have been studied via X‐ray diffraction. The tetraoxazocane ring adopts a boat–chair conformation in the crystalline state, which is due to intramolecular interactions. Conformational analysis of the tetraoxazocane fragment performed at the B3LYP/6‐31G(d,2p) level of theory showed that there are three minima on the potential energy surface, one of which corresponds to the conformation realized in the solid state, but not to a global minimum. Analysis of the geometry and the topological parameters of the electron density at the (3,−1) bond critical points (BCPs), and the charge transfer in the tetraoxazocane ring indicated that there are stereoelectronic effects in the O—C—O and N—C—O fragments. There is a two‐cross hyperconjugation in the N—C—O fragment between the lone electron pair of the N atom (lpN) and the antibonding orbital of a C—O bond (σ*C—O) and vice versa between lpO and σ*C—N. The oxazole substituent has a considerable effect on the geometry and the topological parameters of the electron density at the (3,−1) BCPs of the tetraoxazocane ring. The crystal structure is stabilized via intermolecular C—H…N and C—H…O hydrogen bonds, which is unambiguously confirmed with PIXEL calculations, a quantum theory of atoms in molecules (QTAIM) topological analysis of the electron density at the (3,−1) BCPs and a Hirshfeld analysis of the electrostatic potential. The molecules form zigzag chains in the crystal due to intermolecular C—H…N interactions being electrostatic in origin. The molecules are further stacked due to C—H…O hydrogen bonds. The dispersion component in the total stabilization energy of the crystal lattice is 68.09%.

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Section: Conformational Analysismentioning

confidence: 84%

Section: Molecular Structurementioning

confidence: 93%

Section: Tablementioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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How the oxazole fragment influences the conformation of the tetraoxazocane ring in a cyclohexanespiro-3′-(1,2,4,5,7-tetraoxazocane): single-crystal X-ray and theoretical study

et al. 2019

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Multicomponent Assembly of Bicyclic Aza-peroxides Catalyzed by Samarium Complexes and Their Cytotoxic Activity

Makhmudiyarova,

Ishmukhametova,

Tyumkina

et al. 2023

J. Org. Chem.

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An original strategy toward bridged tetraoxazaspirobicycloalkanes was developed. The synthesis is based on a three-component condensation–cyclization reaction of primary arylamines with 1,1′-peroxybis (1-hydroperoxycycloalkanes) and pentane-1,5-dial catalyzed by Sm(NO3)3·6H2O. The structures and conformations of the products were determined by X-ray diffraction analysis and 1H and 13C NMR spectroscopy. High cytotoxic activity and biological potential toward ferroptosis induction were found for the synthesized bicyclic aza-peroxides.

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Synthesis and anticancer activity novel dimeric azatriperoxides

et al. 2019

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An efficient method was developed for the synthesis of tetra(spirocycloalkane)-substituted a,udi (1,2,4,5,7,8-hexaoxa-10-azacycloundecan-10-yl)alkanes by a ring transformation reaction of 3,6di(spirocycloalkane)-substituted 1,2,4,5,7,8,10-heptaoxacycloundecanes with a,u-alkanediamines (1,4butane-, 1,5-pentane-, 1,7-heptane-, 1,8-octane-and 1,10-decanediamines) catalyzed by Sm(NO 3 ) 3 /g-Al 2 O 3 . Using flow cytometry, it was shown for the first time that synthesized dimeric azatriperoxides are efficient apoptosis inducers with Jurkat, K562, U937, and Hek296.Scheme 1 Synthesis of a,u-bis-(1,2,4,5,7,8-hexaoxa-10-azacycloundecan-10-yl)alkanes.

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What is responsible for conformational diversity in single-crystal tetraoxazaspiroalkanes? X-Ray, DFT, and AIM approaches

Abstract: The conformational diversity of single crystal tetraoxazaspiroalkanes is considered for the first time with X-ray, DFT, and AIM approaches.

Cited by 5 publications

References 47 publications

How the oxazole fragment influences the conformation of the tetraoxazocane ring in a cyclohexanespiro-3′-(1,2,4,5,7-tetraoxazocane): single-crystal X-ray and theoretical study

How the oxazole fragment influences the conformation of the tetraoxazocane ring in a cyclohexanespiro-3′-(1,2,4,5,7-tetraoxazocane): single-crystal X-ray and theoretical study

Multicomponent Assembly of Bicyclic Aza-peroxides Catalyzed by Samarium Complexes and Their Cytotoxic Activity

Synthesis and anticancer activity novel dimeric azatriperoxides

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