Stereoselective Synthesis of Bridged Azepine Derivatives via Polyfunctionalized Spiroannulated Thiophene. Novel Rearrangement of Oxime Esters

Bogdanowicz-Szwed, Krystyna; Grochowski, J.; Obara, Agnieszka; Ryś, Barbara; Serda, Paweł

doi:10.1021/jo010349k

Cited by 19 publications

(10 citation statements)

References 16 publications

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“…Apart from the signals of the aryl protons the 1 H NMR spectra contain signals of the amino group in the region of 7.39-7.52 ppm, close to the data obtained for 2-amino-3-cyano-4,5-dihydrothiophenes (7.12-7.30 ppm) [11]. Compounds 3a-f and 4a-e are characterized by signals for the H-4 protons in the region of 5.01-5.39 ppm, observed in 3-aroyl-4-aryl-2-arylamino-5-hydroxyimino-4,5-dihydrothiophenes [16,17]. The spectra also contain broad singlets for the OH groups in the range of 11.42-11.58 ppm.…”

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confidence: 85%

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Synthesis of 2-amino-4-aryl-3-cyano-5-hydroxyimino-4,5-dihydrothiophenes

Chunikhin

Rodinovskaya

Шестопалов

2007

Chem Heterocycl Comp

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Aliphatic nitro compounds are of interest as reactive starting materials in the synthesis of heterocycles both with and without a nitro group [1]. We made a systematic study of the reactions of α-carbonyl and α,β-unsaturated nitro compounds with various CH-nucleophiles and determined their regioselectivity, which depends on the structure of the initial compounds and the reaction conditions. It has been shown that the products from the reactions of the nitro compounds with the CH-nucleophiles can be both acyclic compounds and heterocycles of the indolizine, thiophene, and pyridine series [2][3][4][5].We established that the reaction between the nitrostyrenes 1a-e, cyanothioacetamide 2, and an equivalent of tetramethylethylenediamine (TMEDA) or morpholine takes place in ethanol at room temperature with the formation of compounds 3a-f with yields of 30-60%. S Ar N NH 2 B N O H Ar NO 2 3a-f 2 B 1a-e + + NCCH 2 CSNH 2 1a, 3a,f Ar = Ph; 1, 3 b Ar = 4-ClC 6 H 4 , c Ar = 2-C 4 H 3 S, d Ar = 4-FC 6 H 4 , e Ar = 4-MeOC 6 H 4 ; 3 a-e B = 0.5(Me 2 NCH 2 CH 2 NMe 2 ), f B = O N HCompounds 3a-f are complexes of 2-amino-4-aryl-3-cyano-5-hydroxyimino-4,5-dihydrothiophenes with the bases in ratios of 2:1 in the case of TMEDA 3a-e and 1:1 in the case of morpholine 3f. By conducting the reaction in the presence of ethyl ether it is possible to obtain compounds 3a-f with yields of 50-80% [6].Further study of the reaction showed that compounds not containing the base combined into a complex can be isolated. Thus, 2-amino-4-aryl-3-cyano-5-hydroxyimino-4,5-dihydrothiophene 4a is formed with an almost quantitative yield when the nitrostyrene 1a is briefly boiled with cyanothioacetamide 2 in the presence of __________________________________________________________________________________________

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confidence: 85%

“…The reaction of thioamides with nitrostyrenes has hardly been studied at all. Two examples of the reaction of β-nitrostyrenes with N-aryl-substituted thioamides of 3-oxopropionic acids leading to the formation of 3-aroyl-4-aryl-2-arylamino-5-hydroxyimino-4,5-dihydrothiophenes are known [16,17].…”

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Synthesis of 2-amino-4-aryl-3-cyano-5-hydroxyimino-4,5-dihydrothiophenes

Chunikhin

Rodinovskaya

Шестопалов

2007

Chem Heterocycl Comp

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“…6 Bogdanowicz-Szwed and co-workers reported the base-catalyzed reaction of β-ketothioamides with (E)-β-nitrostyrenes which yielded spiro(indane-1,3′-thiophenes). 7,8 On the other hand, the hexahydropyrimidine fragment is present in several natural products and in pharmaceutical agents of various biological activity. [9][10][11][12] Some derivatives of hexahydropyrimidine are used as stabilizers of polymers.…”

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Facile and efficient synthesis of 4'-thioxo-1',3,3',4,4',6' -hexahydro-1H,2'H-spiro[naphthalene-2,5'-pyrimidin]-1-ones in a three-component Mannich-type reaction

Jagodziński¹,

Westerlich²

2013

Arkivoc

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“…[5][6][7] The efficiency of this route prompted us extend this methodology to the synthesis of compounds containing two and three thiophene units. [5][6][7] The efficiency of this route prompted us extend this methodology to the synthesis of compounds containing two and three thiophene units.…”

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confidence: 99%