Priprava i odvajanje enantiomera 2-kinolinonskih epoksida uz regioselektivno otvaranje prstena

master's thesis

• Title (english): Synthesis and enantioseparation of 2-quinolinone epoxides with regioselective ring-opening
• Author: Paola Sinković
• Mentor: Marin Roje (mentor)
• Committee member: Ines Primožič (predsjednik povjerenstva)
• Committee member: Nives Galić (član povjerenstva)
• Committee member: Marijana Đaković (član povjerenstva)
• Committee member: Željka Car (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2021-09-30, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U sklopu diplomskog rada pripravljeno je pet derivata 2-kinolinonskih epoksida. Tri
disupstituirana epoksida dobivena su reakcijom akiralne benzilsulfonijeve soli i odgovarajućeg
aldehida u prisustvu baze, kao smjese cis i trans izomera u dobrom iskorištenju. Ispitan je
utjecaj baze i temperature na iskorištenje i dijastereoselektivnost reakcije te je uočeno da baza
nema bitan utjecaj na dijastereoselektivnost epoksidacije. U svim slučajevima prevladava trans
izomer. Reakcijom izopropil(difenil)sulfonijeve soli i odgovarajućeg aldehida u prisustvu tertbutillitija, pripravljena su dva trisupstituirana epoksida. Na pripravljenoj seriji epoksida ispitani
su uvjeti regioselektivnog otvaranja prstena korištenjem azidnih nukleofila. Uočeno je da se
najbolja konverzija postiže pri povišenim temperaturama u polarnom sustavu otapala te da
regioselektivnost reakcije ovisi o broju supstituenata na epoksidnom prstenu. U drugom dijelu
istraživanja ispitani su uvjeti odjeljivanja enantiomera epoksida na polisaharidnim kiralnim
nepokretnim fazama primjenom visokodjelotvorne tekućinske kromatografije. Najboljim
izborom za odjeljivanje enantiomera pokazala se Chiralpak AD nepokretna faza s tris-(3,5-
dimetilfenilkarbamat) amilozom kao kiralnim selektorom.

Abstract (english)

In this thesis, five derivatives of 2-quinolinone epoxides were prepared. Three disubstituted
epoxides were obtained by reaction between an achiral benzylsulfonium salt and the
corresponding aldehyde in the presence of a base, as a mixture of cis/trans isomers in good
yield. The effect of base and temperature on the yield and diastereoselectivity of the reaction
was investigated. It was observed that base had no significant effect on the diastereoselectivity
of epoxidation. In all cases, the trans isomer predominates. Two trisubstituted epoxides were
prepared by reaction between isopropyl(diphenyl)sulfonium salt and the corresponding
aldehyde in the presence of tert-butyl-lithium. Conditions for regioselective ring-opening were
tested on prepared series of compounds using an azide reagents. It was observed that the best
conversion was achieved at higher temperatures in the polar solvent system. The
regioselectivity of reaction depends on the number of substituents. In the second part of
research, the conditions for the enantioseparation of epoxides on polysaccharide chiral
stationary phases were investigated using high performance liquid chromatography. Chiralpak
AD stationary phase with chiral selector tris-(3,5-dimethylphenylcarbamate) amylose proved to
be the best choice.

• Keywords: azidoliza; epoksidi; 2-kinolinoni; kiralna nepokretna faza; regioselektivnost
• Keywords (english): azidolysis; chiral stationary phases; epoxides; 2-quinolinone; regioselectivity
• Language: croatian
• URN:NBN: urn:nbn:hr:217:389903
• Project: Number: N/A; Title: Znanstveni centar izvrsnosti za bioprospecting mora; Title: Scientific Center of Excellence for Bioprospecting of the sea; Acronym: BioProCro; Leader: Rozelinda Čož-Rakovac; Jurisdiction: Croatia; Funder: MZOS; Funding stream: ZCI
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2022-09-30
• Created on: 2021-10-25 10:41:19