A Diastereoselective Catalytic Approach to Pentasubstituted Pyrrolidines by Tandem Anionic-Radical Cross-Over Reactions

0552859 - ÚOCHB 2023 RIV DE eng J - Článek v odborném periodiku
Hidasová, Denisa - Pohl, Radek - Císařová, I. - Jahn, Ullrich
A Diastereoselective Catalytic Approach to Pentasubstituted Pyrrolidines by Tandem Anionic-Radical Cross-Over Reactions.
Advanced Synthesis & Catalysis. Roč. 364, č. 3 (2022), s. 671-678. ISSN 1615-4150. E-ISSN 1615-4169
Grant CEP: GA ČR GA13-40188S; GA MŠMT(CZ) EF16_019/0000729
Institucionální podpora: RVO:61388963
Klíčová slova: pyrrolidines * asymmetric synthesis * single-electron transfer * Aza-Michael addition * radical reactions
Obor OECD: Organic chemistry
Impakt faktor: 5.4, rok: 2022
Způsob publikování: Open access
https://doi.org/10.1002/adsc.202101172

Pentasubstituted pyrrolidines are ubiquitous constituents of natural products and drugs, however the access options to them especially with respect to absolute and relative stereochemistry are not well developed. We report an asymmetric synthesis of N,2,3,4,5-pentasubstituted pyrrolidines by oxidative single-electron transfer-catalyzed tandem aza-Michael addition/radical 5-exo cyclization/oxygenation reactions. The absolute stereochemistry is set by applying readily accessible chiral allylamines in asymmetric conjugate additions to various β-substituted-α,β-unsaturated esters, which dependent on the substituent R2 sets the configuration of the two stereocenters next to the amine function, whereas two more are diastereoselectively generated by the radical 5-exo cyclization step. This allows the diastereodivergent single-step synthesis of pyrrolidines with four contiguous stereogenic centers. The stereoselectivity is rationalized by a predictive model.
Trvalý link: http://hdl.handle.net/11104/0327955


Vědecká data: CCDC, CCDC, CCDC