Mechanistic insights into annulation of arylidene- [Delta] [sup] 2-pyrrolin-4-ones by cinchona squaramide-based organocatalysts

Ciber, Luka (avtor), Ričko, Sebastijan (avtor), Gregorc, Jure (avtor), Požgan, Franc (avtor), Svete, Jurij (avtor), Brodnik, Helena (avtor), Štefane, Bogdan (avtor), Grošelj, Uroš (avtor)

Arylidene-Δ2-pyrrolin-4-ones undergo organocatalyzed annulation with malononitrile, furnishing dihydropyrano[3,2-b]pyrroles (18 examples, 0–77% ee in dichloromethane, 11–44% ee in methanol). The products could be enantiomerically enriched by trituration (11 examples, 95–99% ee). Enantioselectivity was dependent on the nature of the substrate and the conformation of the catalyst, which in turn was solvent-controlled. The reaction mechanism, which included two pseudo-enantiomeric organocatalyst conformations, was investigated by experimental and quantum chemical methods. The reaction mechanism consists of Michael addition reaction step followed by 6-exo-dig annulation, which was found to be the rate determining step. Additionally, it was identified that the preferred reaction pathway follows the model originally proposed by Pápai et al.

• Jezik: Angleški jezik
• Ključne besede: organocatalysis, asymmetric synthesis, enantioselectivity, solvent effects, pyrrolone, pseudo-enantiomeric catalyst conformations
• Vrsta gradiva: Članek v reviji
• Tipologija: 1.01 - Izvirni znanstveni članek
• Organizacija: FKKT - Fakulteta za kemijo in kemijsko tehnologijo
• Status publikacije: V tisku
• Različica publikacije: Recenzirani rokopis
• Leto izida: 2022
• Št. strani: Str. 1-14
• Številčenje: Vol. 464, iss.
• PID: 20.500.12556/RUL-134970
• UDK: 547.74:544.47
• ISSN pri članku: 1615-4150
• DOI: 10.1002/adsc.202101369
• COBISS.SI-ID: 97278211
• Datum objave v RUL: 15.02.2022

Gradivo je del revije

• Naslov: Advanced synthesis & catalysis
• Založnik: Wiley
• ISSN: 1615-4150
• COBISS.SI-ID: 22726149

Licence

• Licenca: CC BY-NC-ND 4.0, Creative Commons Priznanje avtorstva-Nekomercialno-Brez predelav 4.0 Mednarodna
• Povezava: http://creativecommons.org/licenses/by-nc-nd/4.0/deed.sl
• Opis: Najbolj omejujoča licenca Creative Commons. Uporabniki lahko prenesejo in delijo delo v nekomercialne namene in ga ne smejo uporabiti za nobene druge namene.
• Začetek licenciranja: 14.01.2022

Sekundarni jezik

• Jezik: Slovenski jezik
• Ključne besede: organokataliza, asimetrična sinteza, enantioselektivnost, učinki topil, piroloni, psevdo-enantiomerne konformacije katalizatorja

Projekti

• Financer: ARRS - Agencija za raziskovalno dejavnost Republike Slovenije
• Številka projekta: P1-0179
• Naslov: Napredna organska sinteza in kataliza