Pd/C-КАТАЛІЗОВАНЕ ГІДРУВАННЯ МЕТИЛ ПІРОЛ-3-КАРБОКСИЛАТІВ У ДІАСТЕРЕОСЕЛЕКТИВНОМУ СИНТЕЗІ α-ЗАМІЩЕНИХ β-ПРОЛІНІВ

Pd/C-КАТАЛІЗОВАНЕ ГІДРУВАННЯ МЕТИЛ ПІРОЛ-3-КАРБОКСИЛАТІВ У ДІАСТЕРЕОСЕЛЕКТИВНОМУ СИНТЕЗІ α-ЗАМІЩЕНИХ β-ПРОЛІНІВ

The analysis of synthetic and biological importance of α-substituted β-prolines was conducted. Methods of synthesis of β-prolines and their esters, based on both intra- and intermolecular reactions of formation of functionalized pyrrolidinic cycle, as well as catalytic reduction of corresponding 2,3...

Full description

Saved in:
Bibliographic Details
Date:2020
Main Authors: Kemskiy, Sergiy, Grozav, Alina, Sujkov, Sergiy, Yurchenko, Oleksandr, Vovk, Mykhailo
Format: Article
Language:English
Published: V.I.Vernadsky Institute of General and Inorganic Chemistry 2020
Online Access:https://ucj.org.ua/index.php/journal/article/view/127
Tags: Add Tag
No Tags, Be the first to tag this record!
Journal Title:Ukrainian Chemistry Journal

Institution

Ukrainian Chemistry Journal
id oai:ojs2.1444248.nisspano.web.hosting-test.net:article-127
record_format ojs
spelling oai:ojs2.1444248.nisspano.web.hosting-test.net:article-1272020-03-18T17:41:07Z Pd/C-CATALISED HYDROGENIZATION OF METHYL PYRROLE-3-CARBOXYLATES IN THE DIASTEREOSELECTIVE SYNTHESIS OF α-SUBSTITUTED β-PROLINES Pd/C-КАТАЛИЗИРОВАННОЕ ГИДРИРОВАНИЕ МЕТИЛ ПИРОЛ-3-КАРБОКСИЛАТОВ В ДИАСТЕРЕО-СЕЛЕКТИВНОМ СИНТЕЗЕ α-ЗАМЕЩЕННЫХ β-ПРОЛИНОВ Pd/C-КАТАЛІЗОВАНЕ ГІДРУВАННЯ МЕТИЛ ПІРОЛ-3-КАРБОКСИЛАТІВ У ДІАСТЕРЕОСЕЛЕКТИВНОМУ СИНТЕЗІ α-ЗАМІЩЕНИХ β-ПРОЛІНІВ Kemskiy, Sergiy Grozav, Alina Sujkov, Sergiy Yurchenko, Oleksandr Vovk, Mykhailo pyrrol-3-carboxylates, Pd/C-catalised hydrogenization, diastereoselective synthesis, β-prolines. The analysis of synthetic and biological importance of α-substituted β-prolines was conducted. Methods of synthesis of β-prolines and their esters, based on both intra- and intermolecular reactions of formation of functionalized pyrrolidinic cycle, as well as catalytic reduction of corresponding 2,3-substituted pyrroles and their dihydro derivatives, were systematized. The necessity of the hydrogenation process improvement of 2,3-di-substituted pyrroles using cheap catalysts was justified. The approach to α-substituted β-prolines (2-substituted pyrrolidine-3-carboxylic acids) was pro-posed, the first stage of which is N-Boc-protection of 2-substituted pyrrolidine-3-carboxylates with di-tert-butyl dicarbonate (Boc-anhydride) in the dichloromethane solution at the room temperature in presence of catalytic amounts of N,N-dime-thylaminopyridine. Obtained derivatives were subjected to hydrogenation in the autoclave at 45 atm. at 40 oC for 20 hours in presence of 10 % Pd/C catalyst. It was found, that reaction at such conditions proceeds with the full conversion of starting compounds and demonstrates high stereoselec-tivity and leads to the mixture of diastereomeric N-Boc-protected pyrrolidine-3-carboxylates of cis- and trans-configurations with corresponding contents of 84–87 % and 13–16 % according to NMR 1Н and chromato-mass spectra. The mild hydrolysis of isolated reaction mixtures in the water solution of lithium hydroxide followed by neutrali-zation and N-Boc-deprotection with 15 % hydrochloric acid allows isolating pure major diaste-reomers of α-substituted β-prolines with 69–74 % yields. Their trans-configuration was reliably confirmed by NMR 1Н spectroscopy using the NOESY experiment. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-02-05 Article Article Organic chemistry Органическая xимия Органічна xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/127 10.33609/0041-6045.86.2.2020.100-110 Ukrainian Chemistry Journal; Vol. 86 No. 2 (2020): Ukrainian Chemistry Journal; 100-110 Украинский химический журнал; Том 86 № 2 (2020): Украинский химический журнал; 100-110 Український хімічний журнал; Том 86 № 2 (2020): Український хімічний журнал; 100-110 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/127/82
institution Ukrainian Chemistry Journal
baseUrl_str
datestamp_date 2020-03-18T17:41:07Z
collection OJS
language English
topic_facet pyrrol-3-carboxylates
Pd/C-catalised hydrogenization
diastereoselective synthesis
β-prolines.
format Article
author Kemskiy, Sergiy
Grozav, Alina
Sujkov, Sergiy
Yurchenko, Oleksandr
Vovk, Mykhailo
spellingShingle Kemskiy, Sergiy
Grozav, Alina
Sujkov, Sergiy
Yurchenko, Oleksandr
Vovk, Mykhailo
Pd/C-КАТАЛІЗОВАНЕ ГІДРУВАННЯ МЕТИЛ ПІРОЛ-3-КАРБОКСИЛАТІВ У ДІАСТЕРЕОСЕЛЕКТИВНОМУ СИНТЕЗІ α-ЗАМІЩЕНИХ β-ПРОЛІНІВ
author_facet Kemskiy, Sergiy
Grozav, Alina
Sujkov, Sergiy
Yurchenko, Oleksandr
Vovk, Mykhailo
author_sort Kemskiy, Sergiy
title Pd/C-КАТАЛІЗОВАНЕ ГІДРУВАННЯ МЕТИЛ ПІРОЛ-3-КАРБОКСИЛАТІВ У ДІАСТЕРЕОСЕЛЕКТИВНОМУ СИНТЕЗІ α-ЗАМІЩЕНИХ β-ПРОЛІНІВ
title_short Pd/C-КАТАЛІЗОВАНЕ ГІДРУВАННЯ МЕТИЛ ПІРОЛ-3-КАРБОКСИЛАТІВ У ДІАСТЕРЕОСЕЛЕКТИВНОМУ СИНТЕЗІ α-ЗАМІЩЕНИХ β-ПРОЛІНІВ
title_full Pd/C-КАТАЛІЗОВАНЕ ГІДРУВАННЯ МЕТИЛ ПІРОЛ-3-КАРБОКСИЛАТІВ У ДІАСТЕРЕОСЕЛЕКТИВНОМУ СИНТЕЗІ α-ЗАМІЩЕНИХ β-ПРОЛІНІВ
title_fullStr Pd/C-КАТАЛІЗОВАНЕ ГІДРУВАННЯ МЕТИЛ ПІРОЛ-3-КАРБОКСИЛАТІВ У ДІАСТЕРЕОСЕЛЕКТИВНОМУ СИНТЕЗІ α-ЗАМІЩЕНИХ β-ПРОЛІНІВ
title_full_unstemmed Pd/C-КАТАЛІЗОВАНЕ ГІДРУВАННЯ МЕТИЛ ПІРОЛ-3-КАРБОКСИЛАТІВ У ДІАСТЕРЕОСЕЛЕКТИВНОМУ СИНТЕЗІ α-ЗАМІЩЕНИХ β-ПРОЛІНІВ
title_sort pd/c-каталізоване гідрування метил пірол-3-карбоксилатів у діастереоселективному синтезі α-заміщених β-пролінів
title_alt Pd/C-CATALISED HYDROGENIZATION OF METHYL PYRROLE-3-CARBOXYLATES IN THE DIASTEREOSELECTIVE SYNTHESIS OF α-SUBSTITUTED β-PROLINES
Pd/C-КАТАЛИЗИРОВАННОЕ ГИДРИРОВАНИЕ МЕТИЛ ПИРОЛ-3-КАРБОКСИЛАТОВ В ДИАСТЕРЕО-СЕЛЕКТИВНОМ СИНТЕЗЕ α-ЗАМЕЩЕННЫХ β-ПРОЛИНОВ
description The analysis of synthetic and biological importance of α-substituted β-prolines was conducted. Methods of synthesis of β-prolines and their esters, based on both intra- and intermolecular reactions of formation of functionalized pyrrolidinic cycle, as well as catalytic reduction of corresponding 2,3-substituted pyrroles and their dihydro derivatives, were systematized. The necessity of the hydrogenation process improvement of 2,3-di-substituted pyrroles using cheap catalysts was justified. The approach to α-substituted β-prolines (2-substituted pyrrolidine-3-carboxylic acids) was pro-posed, the first stage of which is N-Boc-protection of 2-substituted pyrrolidine-3-carboxylates with di-tert-butyl dicarbonate (Boc-anhydride) in the dichloromethane solution at the room temperature in presence of catalytic amounts of N,N-dime-thylaminopyridine. Obtained derivatives were subjected to hydrogenation in the autoclave at 45 atm. at 40 oC for 20 hours in presence of 10 % Pd/C catalyst. It was found, that reaction at such conditions proceeds with the full conversion of starting compounds and demonstrates high stereoselec-tivity and leads to the mixture of diastereomeric N-Boc-protected pyrrolidine-3-carboxylates of cis- and trans-configurations with corresponding contents of 84–87 % and 13–16 % according to NMR 1Н and chromato-mass spectra. The mild hydrolysis of isolated reaction mixtures in the water solution of lithium hydroxide followed by neutrali-zation and N-Boc-deprotection with 15 % hydrochloric acid allows isolating pure major diaste-reomers of α-substituted β-prolines with 69–74 % yields. Their trans-configuration was reliably confirmed by NMR 1Н spectroscopy using the NOESY experiment.
publisher V.I.Vernadsky Institute of General and Inorganic Chemistry
publishDate 2020
url https://ucj.org.ua/index.php/journal/article/view/127
work_keys_str_mv AT kemskiysergiy pdccatalisedhydrogenizationofmethylpyrrole3carboxylatesinthediastereoselectivesynthesisofasubstitutedbprolines
AT grozavalina pdccatalisedhydrogenizationofmethylpyrrole3carboxylatesinthediastereoselectivesynthesisofasubstitutedbprolines
AT sujkovsergiy pdccatalisedhydrogenizationofmethylpyrrole3carboxylatesinthediastereoselectivesynthesisofasubstitutedbprolines
AT yurchenkooleksandr pdccatalisedhydrogenizationofmethylpyrrole3carboxylatesinthediastereoselectivesynthesisofasubstitutedbprolines
AT vovkmykhailo pdccatalisedhydrogenizationofmethylpyrrole3carboxylatesinthediastereoselectivesynthesisofasubstitutedbprolines
AT kemskiysergiy pdckatalizirovannoegidrirovaniemetilpirol3karboksilatovvdiastereoselektivnomsintezeazameŝennyhbprolinov
AT grozavalina pdckatalizirovannoegidrirovaniemetilpirol3karboksilatovvdiastereoselektivnomsintezeazameŝennyhbprolinov
AT sujkovsergiy pdckatalizirovannoegidrirovaniemetilpirol3karboksilatovvdiastereoselektivnomsintezeazameŝennyhbprolinov
AT yurchenkooleksandr pdckatalizirovannoegidrirovaniemetilpirol3karboksilatovvdiastereoselektivnomsintezeazameŝennyhbprolinov
AT vovkmykhailo pdckatalizirovannoegidrirovaniemetilpirol3karboksilatovvdiastereoselektivnomsintezeazameŝennyhbprolinov
AT kemskiysergiy pdckatalízovanegídruvannâmetilpírol3karboksilatívudíastereoselektivnomusintezíazamíŝenihbprolínív
AT grozavalina pdckatalízovanegídruvannâmetilpírol3karboksilatívudíastereoselektivnomusintezíazamíŝenihbprolínív
AT sujkovsergiy pdckatalízovanegídruvannâmetilpírol3karboksilatívudíastereoselektivnomusintezíazamíŝenihbprolínív
AT yurchenkooleksandr pdckatalízovanegídruvannâmetilpírol3karboksilatívudíastereoselektivnomusintezíazamíŝenihbprolínív
AT vovkmykhailo pdckatalízovanegídruvannâmetilpírol3karboksilatívudíastereoselektivnomusintezíazamíŝenihbprolínív
first_indexed 2025-09-24T17:43:24Z
last_indexed 2025-09-24T17:43:24Z
_version_ 1849658073636929536

Similar Items