ChemInform Abstract: Synthesis of 1,5‐Dinitro‐3‐azabicyclo[3.3.1]non‐6‐ene Derivatives.

Atroshchenko, Yu. M.; Nikiforova, E. G.; Gitis, S. S.; Grudtsyn, Yu. D.; Шишкин, Олег В.; Andrianov, V. F.; Shakhkel'dyan, I. V.

doi:10.1002/chin.200038176

Cited by 3 publications

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“…Products formally involving double N D Ar reactions have been reported. The anions resulting either through borohydride reduction or enolate addition to nitroarenes have been trapped via Mannich reaction with formaldehyde and primary diamines to give bis(3-azabicyclo[3.3.1]nonanes) linked through a methylene bridge, generally in low yields . Genuine examples of double N D Ar reactions are the coupling of 9-anthracenediazonium salts with the amine precursors 22 and the bis-adduct formed in the reaction of the Grignard reagent of 1,8-bis(chloromethyl)naphthalene with 9-trimethylsilylanthracene .…”

Section: Resultsmentioning

confidence: 99%

Double Dearomatization of Bis(diphenylphosphinamides) through Anionic Cyclization. A Facile Route of Accessing Multifunctional Systems with Antitumor Properties

et al. 2007

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The sequential one-pot double dearomatization of bis(N-benzyl-P,P-diphenylphosphinamides) via anionic cyclization is described for the first time. Protonation and alkylation of the dearomatized dianions provide bis(tetrahydro-2,1-benzazaphospholes) in good yield and with very high regio- and stereocontrol. Acid-catalyzed methanolysis of the bisheterocycles affords bis(methyl gamma-aminophosphinates) stereospecifically. The doubly phosphorylated systems proved to be active against a series of cancer cell lines.

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Section: Resultsmentioning

confidence: 99%

Double Dearomatization of Bis(diphenylphosphinamides) through Anionic Cyclization. A Facile Route of Accessing Multifunctional Systems with Antitumor Properties

et al. 2007

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“…Additionally, by using primary diamines in the process, bis-3-ABNs 491 were obtained linked through a hydrocarbon bridge of 2, , 4, , or 6 256 atoms (Scheme ; Table , entries 63−67). In general, yields of mono- and bis-3-ABNs were low.…”

Section: 11 Reactions With Hydride Transfer Agentsmentioning

confidence: 99%

“…253 The azabicyclic system also occurs in the skeleton of several diterpene alkaloids. 254 Following the discovery of the synthesis of 3-ABNs using dinitrobenzenes as starting materials, Wall 255 and, particulary, Atroshchenko and coworkers [256][257][258][259][260][261] demonstrated the wide scope of this reaction by preparing a large series of derivatives through variations in the substituents of the aromatic ring and the use of ammonia and functionalized aliphatic primary amines including haloamines, hydroxyamines, and amino acids. The results are collected in Table 34.…”

Section: Reactions With Hydride Transfer Agentsmentioning

confidence: 99%

Nucleophilic Dearomatizing (D_NAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

et al. 2007

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Institute fu ¨r Kohlenforschung (Mu ¨lheim a.d. Ruhr) with R. Benn investigating 187 Os NMR. In November 1989 he became Profesor Titular at the University of Oviedo, where he started his own research. He moved to the University of Almerı ´a (1996), where he is Professor of Organic Chemistry. His current research activities range from the application of phosphorus-stabilized carbanions in organic and organometallic chemistry to mechanistic studies of reactions involving organometallic species through multinuclear magnetic resonance. G. Ruiz Go ´mez was born in Madrid, Spain. She studied chemistry at the University of Almerı ´a and completed her first degree (Licenciatura) in July 2000. She was awarded a Ph.D. in 2006 for work on dearomatizing reactions of phosphinamides and phosphonamides under the direction of Professor Lo ´pez Ortiz. She is currently a postdoctoral fellow in Professor Lo ´pez-Ortiz's group with interest in the synthesis of non-natural peptides and peptide analogues.

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“…In continuation of investigations [2][3][4][5][6][7][8] on applying anionic σ-adducts of dinitroarenes I to preparation of polyfunctional derivatives of 3-azabicyclo[3.3.1]nonane, an important class of compounds possessing versatile biological activity [9], in the present study syntheses were performed of a series of 6-R-11-R'-1,9-dinitro-5-oxa-11-azatricyclo[6.4.0.0 4,9 ]dodecan-2-ones IIa-IIj. The preparation of compound IIa at reduction of Janovsky σ-adduct of 2,4-dinitrophenol and acetone (Ia) with sodium borohydride was first reported [10], but no reliable proofs of tricyclic compound formation were given.…”

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Synthesis and Structure of 1,9-Dinitro-5-oxa-11-azatricyclo[6.4.0.04,9]dodecan-2-one

et al. 2005

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A series of 6,11-disubstituted 1, 9-dinitro-5-oxa-11-azatricyclo[6.4.0.0 4,9 ]dodecan-2-ones were prepared from anionic adducts of 2,4-dinitrophenol with propanone and 2-phenylethanone carbanions by successive selective reduction with sodium borohydride and aminomethylation with formaldehyde and primary amines. By spectral methods and by quantum-chemical calculations following PM3 method the structure of the molecules synthesized was shown to contain all the three rings in a chair form with equatorial substituents in positions 6 and 11.Nitroarenes are fairly often involved in the synthesis of polyfunctional N,O-heterocyclic compounds possessing quite a number of useful properties [1]. In continuation of investigations [2-8] on applying anionic σ-adducts of dinitroarenes I to preparation of polyfunctional derivatives of 3-azabicyclo[3.3.1]nonane, an important class of compounds possessing versatile biological activity [9], in the present study syntheses were performed of a series of 6-R-11-R'-1,9-dinitro-5-oxa-11-azatricyclo[6.4.0.0 4,9 ]dodecan-2-ones IIa-IIj. The preparation of compound IIa at reduction of Janovsky σ-adduct of 2,4-dinitrophenol and acetone (Ia) with sodium borohydride was first reported [10], but no reliable proofs of tricyclic compound formation were given. Therefore we carried out a more detailed investigation of the molecular structure of compounds synthesized by means of NMR spectroscopy.The reduction of carbonyl group in oxopropyl and 2-phenyloxoethyl substituents in the Janovsky adducts Ia and Ib was performed with the use of NaBH 4 . This reagent of high chemoselectivity is commonly used for selective reduction of an isolated carbonyl group of a saturated ketone in the presence of a conjugated C=O bond [11]. The forming intermediate secondary alcohols A without separation from the reaction mixture were brought into the Mannich condensation with primary amines and formaldehyde. As a result we obtained in 50-70% yields N,O-containing tricyclic compounds IIaIIj. The maximum yield of the compounds was obtained in a mixture MeCN-water at 20°C and the solution pH 6.0.The structure of 6-R-11-R'-1,9-dinitro-5-oxa-11-azatricyclo[6.4.0.0 4,9 ]dodecan-2-ones IIa-IIj is confirmed by the presence in their IR spectra of strong absorption bands in the region 1545-1550 and 1340-1365 cm -1 corresponding to the stretching vibrations of nitro groups. The vibrations of the C=O bond of the endocyclic keto group give rise to absorption in the region 1725-1755 cm -1 . The absorption band at lower frequencies (1085-1145 cm -1 ) belongs to the stretching vibrations of the ether group COC in pyran ring.The assignment of the signals in the NMR spectra of compounds synthesized was done with the help of twodimensional homo-(COSY, NOESY) and heteronuclear (HSQC, HMBC) spectroscopy ensuring the reliable proof of the structure and conformation of the compounds. For instance, in the 1 H NMR spectrum of compound IIa appear 11 signals of chemically or magnetically nonequivalent protons, and in the 13 C NMR spectrum signals...

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ChemInform Abstract: Synthesis of 1,5‐Dinitro‐3‐azabicyclo[3.3.1]non‐6‐ene Derivatives.

Cited by 3 publications

References 0 publications

Double Dearomatization of Bis(diphenylphosphinamides) through Anionic Cyclization. A Facile Route of Accessing Multifunctional Systems with Antitumor Properties

Double Dearomatization of Bis(diphenylphosphinamides) through Anionic Cyclization. A Facile Route of Accessing Multifunctional Systems with Antitumor Properties

Nucleophilic Dearomatizing (D_NAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

Synthesis and Structure of 1,9-Dinitro-5-oxa-11-azatricyclo[6.4.0.04,9]dodecan-2-one

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ChemInform Abstract: Synthesis of 1,5‐Dinitro‐3‐azabicyclo[3.3.1]non‐6‐ene Derivatives.

Cited by 3 publications

References 0 publications

Double Dearomatization of Bis(diphenylphosphinamides) through Anionic Cyclization. A Facile Route of Accessing Multifunctional Systems with Antitumor Properties

Double Dearomatization of Bis(diphenylphosphinamides) through Anionic Cyclization. A Facile Route of Accessing Multifunctional Systems with Antitumor Properties

Nucleophilic Dearomatizing (DNAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

Synthesis and Structure of 1,9-Dinitro-5-oxa-11-azatricyclo[6.4.0.04,9]dodecan-2-one

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Nucleophilic Dearomatizing (D_NAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis