Sinteza pirolonskih derivatov in njihova uporaba v organokataliziranih reakcijah

Ciber, Luka (author), Grošelj, Uroš (mentor)

Iz poceni in lahko dostopnih gradnikov sem pripravil različne benzilidenske pirolin-4-onske derivate z namenom uporabe v nadaljnjih stereoselektivnih organokataliziranih reakcijah. Kljub temu, da je sinteza podobnih spojin literaturno opisana, so se sinteze benzaldehidnih derivatov pirolin-4-onov izkazale za težavne. Uspešno sem optimiziral sintezo benzilidiranih pirolin-4-onov, kar omogoča enostavno pripravo večjih količin teh spojin. Izvedel sem dvostopenjsko enolončno organokatalizirano asimetrično sulfa-Michaelovo/aldolno kaskadno reakcijo. Raznovrstne arilidenske pirolin-4-one sem v prisotnosti kininskega organokatalizatorja reagiral z 1,4-ditian-2,5-diolom do nastanka ustreznih spirocikličnih pirolin-4-onov. Reakcija omogoča tvorbo treh stereogenih centrov od tega je en kvarterni spirostereocenter. Reakcija se je izkazala z relativno visoko diastereoselektivnostjo (73:15:12 – 93:7 d.r.) in enantioselektivnostjo (66 % – >99 % e.e.). Reakcijo tvorbe spirocikličnih pirolin-4-onov sem preizkusil tudi z drugimi, manj pogosto uporabljenimi kininskimi organokatalizatorji. Z njimi in dodatnimi kontrolnimi eksperimenti sem preveril vpliv različnih načinov izolacije na končni enantiomerni presežek produkta.

• Language: Slovenian
• Keywords: pirolin-4-oni, spirociklični pirolin-4-oni, organokataliza, kaskadne reakcije, bifunkcionalni nekovalentni organokatalizatorji
• Work type: Master's thesis/paper
• Typology: 2.09 - Master's Thesis
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Year: 2019
• PID: 20.500.12556/RUL-121786
• COBISS.SI-ID: 1538276803
• Publication date in RUL: 29.10.2020

CIBER, Luka, 2019, Sinteza pirolonskih derivatov in njihova uporaba v organokataliziranih reakcijah [online]. Master’s thesis. [Accessed 30 June 2025]. Retrieved from: https://repozitorij.uni-lj.si/IzpisGradiva.php?lang=eng&id=121786

Secondary language

• Language: English
• Title: Synthesis of pyrrolin-4-one derivatives and their application in organocatalyzed reactions

Abstract

Starting from cheap, easily available building blocks, different benzylidene pyrrolin-4-one derivatives were prepared for the application in stereoselective organocatalyzed reactions. Although the synthesis of similar compounds was known from the literature, much effort was employed to successfully optimize synthesis of various benzylidene pyrrolin-4-one derivatives. Under optimized reaction conditions large scale preparation of benzylidenic pyrrolin-4-one heterocycles was enabled. One-pot two-step organocatalyzed asymmetric sulfa-Michael/aldol cascade reactions were performed. Various arylidene pyrrolin-4-one derivatives were reacted with 1,4-ditian-2,5-diol in the presence of a quinine organocatalyst. The product of this reaction were new spirocyclic pyrrolin-4-ones. The reaction enables the construction of three new stereocenters, one of which is a quaternary spiro-stereocenter. Reactions proceeded with relatively high diastereoselectivity (73:15:12 – 93:7 d.r.) and enantioselectivity (66 % – >99 % e.e.). Formation of novel spirocyclic pyrrolin-4-ones was tested also with additional, less frequently applied quinine organocatalysts. With this additional organocatalysts and control experiments, the effect on enantiomeric excess under different isolation procedures was investigated.

• Keywords: pyrrolin-4-ones, spirocyclic pyrrolin-4-ones, organocatalysis, cascade reactions, bifunctional noncovalent organocatalysts