Synthesis of Diastereomeric Spirocyclic Nitroxyl Radicals of 3-Imidazoline Series with Two Mesogenic Groups

Zaitseva, E. V.; Shernyukov, Аndrey V.; Amitina, S. A.; Tamura, Rui; Григорьев, И. А.; Mazhukin, Dmitrii G.

doi:10.1007/s10593-014-1571-7

Cited by 3 publications

(7 citation statements)

References 30 publications

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“…In this regard, first, we describe the preparation and structural characterization of novel nitroxides 4 and 5. Condensation of commercially available 4-(4-hydroxyphenyl)cyclohexanone (6) with 1-(4-benzyloxyphenyl)-2-(hydroxylamino)-2-methylpropan-1-one (5) 35 possessing a protected phenolic group proceeded with high stereoselectivity and quantitatively led to a single isomer of 7. The stereochemistry of 7 was determined by comparing its 1 H and 13 C NMR spectra with those recorded for compound 8.…”

Section: Resultsmentioning

confidence: 99%

“…The synthesis of the next paramagnetic phenol 5 was started from spiro-fused derivative 11 prepared as a diastereomeric mixture by a previously described synthetic procedure. 35 The subsequent Mitsunobu acylation reaction with 3,4,5-tris(dodecyloxy)benzoic acid and separation of obtained isomers cis-12 and trans-12 by preparative thin-layer chromatography (TLC) on silica gel afforded the individual compounds cis-12 and trans-12 in the ratio 5.7:1.0. To confirm the spatial structure of the obtained isomers, they were reduced in aqueous tetrahydrofuran (THF) to the corresponding diamagnetic N-hydroxy derivatives cis-13 and trans-13 by means of a Zn/NH4Cl system.…”

Section: Resultsmentioning

confidence: 99%

“…33 The present report continues our research on the synthesis of functional derivatives of spirocyclic monoand oligoradicals of the azole series. [34][35][36] The present paper describes the synthesis as well as structural characterization of new paramagnetic derivatives of 2,4,6-tris(aryloxy)-1,3,5-triazine (1a-c) and of 2,4bis(aryloxy)-6-methoxy-1,3,5-triazine (2a-c; Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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The synthesis of new functionalized 1,3,5-triazine-based stable bi- and trinitroxides of the 2,5-dihydroimidazole series

Zaytseva¹,

Gatilov²,

Mazhukin³

2018

Arkivoc

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New non-conjugated functionalized 2,5-dihydroimidazole-type bi-and trinitroxyl radicals are described. The synthesis of which was based on a nucleophilic substitution reaction between 2,4,6-trichloro-1,3,5-triazine or 2,4-dichloro-6-methoxy-1,3,5-triazine and spiro-fused 2,5-dihydroimidazole-type monoradicals bearing both a p-hydroxyaryl moiety at the C-4 atom of the heterocycle and a residue at the fourth position of the cyclohexane ring. The model tris-nitroxide with an unsubstituted cyclohexane unit was structurally characterized in the solid state.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The synthesis of new functionalized 1,3,5-triazine-based stable bi- and trinitroxides of the 2,5-dihydroimidazole series

Zaytseva¹,

Gatilov²,

Mazhukin³

2018

Arkivoc

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“…HAK 250 (R = H), bearing an additional functional phenolic group, has been employed for the synthesis of SNRs possessing one or two mesogenic groups. For this purpose, compounds 250 (R = H, C n H 2n+1 ) are condensed with a cycloxexanone [ 157 ] or with its four-substituted functional derivatives, 4-(4-hydroxyphenyl)cyclohexanone [ 158 ] and 4-hydroxycyclohexanone [ 159 ]. After the oxidation of intermediate N -hydroxy derivatives to SNRs 251 , the latter are acylated by means of one or two residues of 4-alkoxybenzoic acids to form corresponding paramagnetic esters 252 (one of examples is shown in Scheme 44 ).…”

Section: 25-dihydroimidazole (3-imidazoline)-type Snrsmentioning

confidence: 99%

Spirocyclic Nitroxides as Versatile Tools in Modern Natural Sciences: From Synthesis to Applications. Part I. Old and New Synthetic Approaches to Spirocyclic Nitroxyl Radicals

Zaytseva

Mazhukin

2021

Molecules

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Spirocyclic nitroxyl radicals (SNRs) are stable paramagnetics bearing spiro-junction at α-, β-, or γ-carbon atom of the nitroxide fragment, which is part of the heterocyclic system. Despite the fact that the first representatives of SNRs were obtained about 50 years ago, the methodology of their synthesis and their usage in chemistry and biochemical applications have begun to develop rapidly only in the last two decades. Due to the presence of spiro-function in the SNRs molecules, the latter have increased stability to various reducing agents (including biogenic ones), while the structures of the biradicals (SNBRs) comprises a rigid spiro-fused core that fixes mutual position and orientation of nitroxide moieties that favors their use in dynamic nuclear polarization (DNP) experiments. This first review on SNRs will give a glance at various strategies for the synthesis of spiro-substituted, mono-, and bis-nitroxides on the base of six-membered (piperidine, 1,2,3,4-tetrahydroquinoline, 9,9′(10H,10H′)-spirobiacridine, piperazine, and morpholine) or five-membered (2,5-dihydro-1H-pyrrole, pyrrolidine, 2,5-dihydro-1H-imidazole, 4,5-dihydro-1H-imidazole, imidazolidine, and oxazolidine) heterocyclic cores.

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“…In this sense, RM1 semiempirical method was employed to evaluate various conformer possibilities of organic compounds that are formed during chemical reactions. [66][67][68][69]73,80,86,87,90,95,96 The energetic properties, such as enthalpy of formation, are very important in the conformer studies, as will be shown in the next section.…”

Section: Structural and Spectroscopic Propertiesmentioning

confidence: 99%

RM1 Semiempirical Model: Chemistry, Pharmaceutical Research, Molecular Biology and Materials Science

Lima¹,

Rocha²,

Freire³

et al. 2018

J. Braz. Chem. Soc.

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In this review, we show improvements to the semiempirical quantum chemical method RM1 and present a wide range of its applications as reported by researchers of various areas, such as theoretical, organic, physical, analytical, and inorganic chemistry, as well as their interfaces with medicinal chemistry, biology, and materials science. Success of RM1 is seemingly due to its ability to predict structural, energetic, electronic and wave function dependent properties of the investigated systems, coupled with its low computational demand required to perform calculations when compared to ab initio and density functional methods. Moreover, RM1 is widely available in several computational chemistry softwares, such as MOPAC, GAMESS, Amber, Spartan, HyperChem, and AMPAC. This review describes various case studies that perhaps can be of interest to researchers who might need a more solid basis from which to expand the frontier of applicability of RM1 to even more complex problems on larger systems.

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Synthesis of Diastereomeric Spirocyclic Nitroxyl Radicals of 3-Imidazoline Series with Two Mesogenic Groups

Cited by 3 publications

References 30 publications

The synthesis of new functionalized 1,3,5-triazine-based stable bi- and trinitroxides of the 2,5-dihydroimidazole series

The synthesis of new functionalized 1,3,5-triazine-based stable bi- and trinitroxides of the 2,5-dihydroimidazole series

Spirocyclic Nitroxides as Versatile Tools in Modern Natural Sciences: From Synthesis to Applications. Part I. Old and New Synthetic Approaches to Spirocyclic Nitroxyl Radicals

RM1 Semiempirical Model: Chemistry, Pharmaceutical Research, Molecular Biology and Materials Science

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