Stereodirected Synthesis of Alkaloid-Like Quinolizidine Systems Научная публикация
Журнал |
Natural Product Research
ISSN: 1478-6419 , E-ISSN: 1478-6427 |
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Вых. Данные | Год: 2020, Том: 34, Номер: 2, Страницы: 269-277 Страниц : 9 DOI: 10.1080/14786419.2018.1528588 | ||||||||
Ключевые слова | Cytisine; 5,5-spirobarbituric acid derivatives; T-reactions; hydrolysis; quinolizidine alkaloids; diastereomers; synchrotron X-ray diffraction | ||||||||
Авторы |
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Организации |
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Реферат:
New stereoselective methods for the chemical modification of cytisine based on T-reactions are reported. A reaction of cytisine with 2-chloro-5-nitrobenzaldehyde and followed condensation with 1,3-dimethylbarbituric acid affords N-(5-nitro-2-{1,3-dimethylperhydropyrimidine-2,4,6-trione-5-methynyl})cytisine, which undergoes a cyclization with the tetrahydropyridine ring closure. The cyclization proceeds via two competing routes yielding 5,5-spirobarbituric acid derivatives with 11,19-diaza-pentacyclo[11.7.1.02,11.05,10.014,19]henicosane and 11,15-diazapentacyclo-[11.7.1.02,11.05,10.015,20]henicosane skeletons. The cyclization reaction in solutions afford either 24.25-trans and 15,16-trans isomers or trans and cis isomer mixtures, depending on the specific solvent. Meanwhile, 24,25-cis and 15,16-cis isomers are formed stereoselectively under heterogeneous conditions in water suspensions. Trans-5,5-spirobarbiturates under similar conditions undergo isomerization into more stable cis-analogs by the configuration inversion at the C7 atom. The synthesized 5,5-spirobarbituric acid derivatives were successfully converted into alkaloid-like quinolizidine systems (1R,2R,3R,13S)-7-nitro-18-oxo-11,19-diazapentacyclo[11.7.1.02,11.05,10.014,19] henicosa-5(10),6,8,14,16-pentaene-3-carboxylic acid and (1R,2S,3S,13S)-nitro-16-oxo-11,15-diazapentacyclo[11,7,1.02,11,05,10,015,20]henicosa-5,7,9,17,19-pentaene-3-carboxylic acid and their derivatives via the spiropyrimidine moiety removal by the stereoselective hydrolysis.
The molecular and crystal structures of the target substances were elucidated by X-ray crystallography and NMR.
Библиографическая ссылка:
Krasnov K.A.
, Krasnova A.A.
, Kartsev V.G.
, Dorovatovskii P.V.
, Zubavichus Y.V.
, Dobrokhotova E.V.
, Kultyshkina E.K.
, Khrustalev V.N.
Stereodirected Synthesis of Alkaloid-Like Quinolizidine Systems
Natural Product Research. 2020. V.34. N2. P.269-277. DOI: 10.1080/14786419.2018.1528588 WOS Scopus РИНЦ
Stereodirected Synthesis of Alkaloid-Like Quinolizidine Systems
Natural Product Research. 2020. V.34. N2. P.269-277. DOI: 10.1080/14786419.2018.1528588 WOS Scopus РИНЦ
Даты:
Поступила в редакцию: | 21 апр. 2018 г. |
Принята к публикации: | 23 сент. 2018 г. |
Опубликована online: | 10 нояб. 2018 г. |
Опубликована в печати: | 17 янв. 2020 г. |
Идентификаторы БД:
Web of science | WOS:000533683800009 |
Scopus | 2-s2.0-85057298107 |
РИНЦ | 38611296 |
Chemical Abstracts | 2018:2160198 |
OpenAlex | W2900233247 |