Domino synthesis of 3-amino-8-hydroxy-1,6-dioxo-2,7-diazaspiro[4.4]non-3-ene-4-carbonitriles

Федосеев, С. В.; Ершов, О. В.; Belikov, М. Yu.; Липин, К. В.; Бардасов, И. Н.; Насакин, О. Е.; Тафеенко, В. А.

doi:10.1016/j.tetlet.2013.02.043

Cited by 36 publications

(12 citation statements)

References 21 publications

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“…The carbonyl group, through the formation of hemiketal ( A ), became a source of a hydroxy group that cyclized regiospecifically to the spatially proximate cyano group and caused the carboxamide formation. CACHE processes are essential for the chemistry of oxonitriles and sometimes can be the reason for unusual quasi-hydrolysis of the cyano group under mild conditions [15,19,23], but it was not mentioned by many authors [28–31]. …”

Section: Resultsmentioning

confidence: 99%

Diastereoselective synthesis of 3,4-dihydro-2H-pyran-4-carboxamides through an unusual regiospecific quasi-hydrolysis of a cyano group

Ievlev

Ершов

Belikov

et al. 2016

Beilstein J. Org. Chem.

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SummaryAn efficient diastereoselective approach for the synthesis of functionalized 3,4-dihydro-2H-pyran-4-carboxamides with variable frame was developed based on the reaction of available 4-oxoalkane-1,1,2,2-tetracarbonitriles (adducts of TCNE and ketones) with aldehydes in an acidic media. An unusual process of quasi hydrolysis of the cyano group was observed in the course of the described regio- and diastereoselective transformation.

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Section: Resultsmentioning

confidence: 99%

Diastereoselective synthesis of 3,4-dihydro-2H-pyran-4-carboxamides through an unusual regiospecific quasi-hydrolysis of a cyano group

Ievlev

Ершов

Belikov

et al. 2016

Beilstein J. Org. Chem.

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“…Carbonyl group, due to the formation of hydrate, takes part as acceptor of water, performs the role of transport and enables intramolecular transfer of water to nearly located cyano group. 7,9,10 CACHE processes are typical for the chemistry of oxonitriles and often can be the reason of an easy addition of water to the cyano group. 9a-d,g-i The evidence of transformation along the way 1 → F → 3 is the formation of pyridine-2-one 3c after the hydrolysis of structural analogue of intermediate F -compound 4 with aqueous mineral acid.…”

Section: Submentioning

confidence: 99%

Domino-synthesis and fluorescence properties of 4-cyano-2-oxo-1,2-dihydropyridine-3-carboxamides and 2-oxo-1,2-dihydropyridine-3,4-dicarbonitriles

et al. 2015

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ARTICLE This journal isNon-catalytic conversion of 4-oxoalkane-1,1,2,2-tetracarbonitriles in presence of water leads to the formation of mixture of fluorescent 4-cyano-2-oxo-1,2-dihydropyridine-3-carboxamides and 2-oxo-1,2-dihydropyridine-3,4-dicarbonitriles in equal proportions. This transformation was explained and spectral-luminescent properties were investigated, fluorescence quantum yield was measured.

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“…37 This is the first case when salts of this type with organic cations have been isolated and characterized, although their presence has been implied at the initial stage of many transformations of 4-oxoalkane-1,1,2,2-tetracarbonitriles in basic media. 35,[38][39][40][41] Compounds 3a-c were found to be unstable in solutions, therefore suitable NMR spectra could not be acquired. The actual spectra contained a multitude of signals, which could not be assigned.…”

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confidence: 99%

Directed synthesis of new spiro-fused photochromes of diarylethene series

Belikov

Ievlev

Belikova

et al. 2015

Chem Heterocycl Comp

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518Diarylethenes (DAE, dihetarylethenes) are subject to intense study due to the possibility of using these compounds as photosensitive components in various applications, in particular, information processing, 1-4 optical switches for organic electronics, 5-7 and biosensors. 8 The potential for practical applications of DAE in the indicated areas motivate synthetic studies of photochromes with precisely designed photophysical parameters, such as thermal stability of the photoinduced form, 9-15 quantum yield of the forward and reverse photoreaction, 16-20 and the phototransformation cyclicity. 21-24 An important direction of study, with the goal of improving the practical characteristics of DAE, is the development of synthetic methods for obtaining DAE with intramolecular noncovalent interactions and steric hindrance. 25-31 One of the methods for creating a non-covalent interaction in DAE is the introduction of spiro-fused structures at the ethene linker. We should note that only isolated examples of spirofused DAE are known. 31-33 However, based on the current data, it is expected that the presence of spiro-fused moiety at the ethene linker could be used to confer certain useful properties to DAE. For example, some of the best forward quantum reaction yields have been demonstrated for spirofused DAE specifically due to the non-covalent interaction, caused by the presence of spirofusion. 31 By introducing or removing spirofusion it may be possible to tune the ability of DAE to undergo photochromic transformations. 32 The introduction of spirofusion may also be used for the preparation of DAE with several photoswitchable fragments. 33 The presented data show the importance of developing new approaches to the synthesis of diarylethenes featuring a rare combination of structural moieties, in particular spiro-fused systems. With this in mind, we set out to expand the range of available methods for the synthesis of DAE with spirofusion at the ethene linker.Recently we demonstrated a new approach to the synthesis of photochromic DAE, based on the transformations of intermediates obtained by reactions of tetracyanoethylene (TCNE) with 1,2-diarylethanones, namely, 3,4-diaryl-4-oxobutane-1,1,2,2-tetracarbonitriles. 34 At the same time, it is known that 4-oxoalkane-1,1,2,2-tetracarbonitriles based on some aliphatic and alkylaromatic ketones react with amines forming spiro compounds, containing an The reaction of tetracyanoethylated 1,2-diarylethanones with morpholine was used for directed synthesis of spiro-fused diarylethenes, 8-amino-1-imino(oxo)-6-morpholino-2-oxa-7-azaspiro[4.4]nona-3,6,8-triene-9-carbonitriles. The intermediates in this process were tetracyanoalkanone salts. The formation of spiranes was sensitive to the nature of aromatic substituents at the carbonyl group of 3,4-diaryl-4-oxobutane-1,1,2,2-tetracarbonitriles. The obtained spiro-fused diarylethenes exhibited photochromic properties.

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Domino synthesis of 3-amino-8-hydroxy-1,6-dioxo-2,7-diazaspiro[4.4]non-3-ene-4-carbonitriles

Cited by 36 publications

References 21 publications

Diastereoselective synthesis of 3,4-dihydro-2H-pyran-4-carboxamides through an unusual regiospecific quasi-hydrolysis of a cyano group

Diastereoselective synthesis of 3,4-dihydro-2H-pyran-4-carboxamides through an unusual regiospecific quasi-hydrolysis of a cyano group

Domino-synthesis and fluorescence properties of 4-cyano-2-oxo-1,2-dihydropyridine-3-carboxamides and 2-oxo-1,2-dihydropyridine-3,4-dicarbonitriles

Directed synthesis of new spiro-fused photochromes of diarylethene series

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