20.500.12556/RUL-164566 Pretvorbe azakinolizinil diazonijevih tetrafluoroboratov s tioli Transformations of azaquinolizinyl diazonium tetrafluoroborates with thiols V sklopu magistrskega dela je bil uspešno razvit in optimiziran fotoredoks-kataliziran pristop sulfanilacije, s katerim je bilo sintetiziranih enajst 3-sulfanil-substituiranih (aza)kinolizinonskih produktov. Kot izhodne spojine so bile uporabljene 4-okso-4H-kinolizin-3- in 4-okso-4H-piridino[1,2-a]pirimidin-3-diazonijeve soli, ki so bile pripravljene po uveljavljenih postopkih iz literature. Ti diazonijevi intermediati so pod fotokemijskimi pogoji reagirali z difenil disulfidom, dimetil disulfidom ali N,N'-bis[(terc-butiloksi)karbonil]-L-cistin dimetil estrom, kar je vodilo do želenih sulfaniliranih produktov. Po analogiji so bile izvedene tudi reakcije s tioli, pri čemer so nastali enaki produkti kot z disulfidnimi reagenti. Oba pristopa sta se izkazala za uspešna, vendar se je metoda z uporabo disulfidov izkazala za bolj učinkovito, saj omogoča sintezo produktov z višjimi izkoristki. Reakcije z nekaterimi tioli so bile izvedene tudi pod termičnimi pogoji, kjer so tioli kot reagenti dosegli boljše rezultate v primerjavi s fotokemijskimi pogoji. Glede na uspešne reakcije diazonijevih soli s cistinom in cisteinom je bila po analogiji izvedena še reakcija z 4-okso-4H-piridino[1,2-a]pirimidin-3-diazonijevim tetrafluoroboratom in proteinom BSA. In this study, a photoredox-catalyzed sulfanylation strategy was developed and optimized, resulting in the successful synthesis of eleven 3-sulfanyl-substituted (aza)quinolizinone products. The key precursors, 4-oxo-4H-quinolizin-3- and 4-oxo-4H-pyrido[1,2-a]pyrimidin-3-diazonium salts, were prepared following well-established literature protocols. These diazonium intermediates underwent photochemical reactions with diphenyl disulfide, dimethyl disulfide, or N,N'-bis[(tert-butoxy)carbonyl]-L-cystine dimethyl ester, leading to the desired sulfanylated products. Additionally, analogous reactions were carried out using thiols, yielding the same products as those obtained with disulfides. While both approaches proved effective, the disulfide-based approach demonstrated superior efficiency, yielding products with higher overall yields. Further, thermal conditions were explored for reactions with certain thiols, where it was observed that thermal activation favoured better yields compared to the photochemical conditions. Based on the successful sulfanylation of diazonium salts with cystine and cysteine, the method was extended to include the reaction of 4-oxo-4H-pyrido[1,2-a]pyrimidin-3-diazonium tetrafluoroborate with the protein BSA. sulfanilacija kinolizini piridino[1 2-a]pirimidini tiazolo[3 2-a]pirimidini fotoredoks kataliza sulfanylation quinolizines pyrido[1 2-a]pyrimidines thiazolo[3 2-a]pyrimidines photoredox catalysis true false false Slovenski jezik Angleški jezik Magistrsko delo/naloga 2024-10-31 00:25:01 2024-10-31 00:25:08 2024-12-20 12:34:11 0000-00-00 00:00:00 2024 0 0 0000-00-00 NiDoloceno NiDoloceno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 24138 220064003 Jurajevcic_Manca_-_Pretvorbe_azakinolizinil_diazonijevih_tetrafluoroboratov_s_tioli.pdf Jurajevcic_Manca_-_Pretvorbe_azakinolizinil_diazonijevih_tetrafluoroboratov_s_tioli.pdf 1 2D2FE47764C7DFED058D5F0FB0379D58 f49bb3e1e395d3ffc8e8b854d2b7598c2aaa215474421ed36863f1d2c747fdf9 e24d1433-9715-11ef-b232-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=195089 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0