20.500.12556/RUL-149531 Fotoredoks arilacije 4-Okso-4H-piridino[1,2-a]pirimidin-3-diazonijevega tetrafluoroborata Photoredox arylations of 4-Oxo-4H-pyridino[1,2-a]pyrimidine-3-diazonium tetrafluoroborate 4-Okso-4H-piridino[1,2-a]pirimidin-3-diazonijev tetrafluoroborat in sorodne heteroaril diazonijeve soli so uporabni reagenti v organski sintezi, ki so splošno dostopni v treh korakih iz alkil 2-acilamino-3-(dimetilamino)propenoatov. V teku raziskave fotoredoks arilacij omenjenih diazonijevih soli sem razvil novo sintezno metodo za pripravo 3-(hetero)aril-substituiranih kinolizinonov in sorodnih kondenziranih pirimidinonov. 2-Aminopiridin, 2-aminotiazol in 2-(piridil)acetonitril sem v ocetni kislini reagiral z 2-acilamino-3-(dimetilamino)propenoatnima reagentoma v 3-benzoilamino-4H-piridino[1,2-a]pirimidin-4-on, 6-(benziloksikarbonil)amino-5H-tiazolo[3,2-a]pirimidin-5-on in 3-(benziloksikarbonil)amino-1-ciano-4H-kinolizin-4-on. Benzoilno zaščitno skupino sem v primeru piridino[1,2-a]pirimidinona odstranil s kislo hidrolizo s klorovodikovo kislino, benziloksikarbonilno zaščitno skupino pa sem v primeru tiazolo[3,2-a]pirimidinona ter 1-cianokinolizinona odstranil z acidolizo z bromovodikovo kislino. Dobljene amine sem nato s tetrafluoroborovo kislino in natrijevim nitritom pretvoril v aril diazonijeve tetrafluoroborate. Po uspešni optimizaciji reakcijskih pogojev sem v prisotnosti dinatrijeve soli eozina Y kot fotokatalizatorja z obsevanjem reakcijske zmesi z zeleno svetlobo uspešno ariliral diazonijeve tetrafluoroborate s (hetero)areni, kot so furan, tiofen, N-Boc-pirol, 2-metilfuran, ferocen, benzen, benzo[b]tiofen in benzo[b]furan. Fotoredoks arilacije sem izvedel v zmesi acetonitrila in deionizirane vode, kar mi je omogočilo preprosto izolacijo končnih produktov s kolonsko kromatografijo. Poleg tega sem med raziskovanjem obsega reakcije študiral tudi mehanizem pretvorbe arilacije diazonijevih tetrafluoroboratov. Glede na dobljene rezultate sem predpostavil radikalski potek transformacije. 4-Oxo-4H-pyridino[1,2-a]pyrimidine-3-diazonium tetrafluoroborate and related heteroaryl diazonium salts are useful reagents in organic synthesis, which are readily available in three steps from alkyl 2-acylamino-3-(dimethylamino)propenoates. In the course of this study on photoredox arylations of title diazonium salts, a novel synthetic method for the preparation of 3-(hetero)aryl-substituted quinolizinones and related fused pyrimidinones was developed. 2-Aminopyridine, 2-aminothiazole and 2-(pyridyl)acetonitrile were reacted in acetic acid with 2-acylamino-3-(dimethylamino)propenoate reagents to yield 3-benzoylamino-4H-pyridino[1,2-a]pyrimidin-4-one, 6-(benzyloxycarbonyl)amino-5H-thiazolo[3,2-a]pyrimidin-4-one and 3-(benzyloxycarbonyl)amino-1-cyano-4H-quinolizin-4-one. The benzoyl protecting group in the case of pyridino[1,2-a]pyrimidinone was removed with hydrochloric acid via acid hydrolysis and benzyloxycarbonyl protecting group in the case of thiazolo[3,2-a]pyrimidinone and 1-cyanoquinolizinone was removed with hydrobromic acid via acidolysis. The obtained amines were then converted into aryl diazonium tetrafluoroborates by the addition of tetrafluoroboric acid and sodium nitrite. After optimizing the reaction conditions, diazonium tetrafluoroborates were successfully arylated with (hetero)arenes, such as furan, thiophene, N-Boc-pyrrole, 2-methylfuran, ferrocene, benzene, benzo[b]thiophene and benzo[b]furan. The arylations were facilitated by the irradiation of the reaction mixture with green light in the presence of eosin Y disodium salt as a photocatalyst. The reactions were performed in a mixture of acetonitrile and deionized water, allowing easy isolation of the final products by column chromatography. Furthermore, while the scope of the reaction was investigated, the mechanism of arylation of diazonium tetrafluoroborates was also studied. Based on the obtained results, radical mechanism of photoredox arylations was proposed. aril diazonijev tetrafluoroborat fotokatalizator svetloba (hetero)aren aryldiazonium tetrafluoroborate photocatalyst light (hetero)arene true false false Slovenski jezik Angleški jezik Magistrsko delo/naloga 2023-09-07 11:26:22 2023-09-07 11:26:23 2023-09-13 10:28:44 0000-00-00 00:00:00 2023 0 0 0000-00-00 NiDoloceno NiDoloceno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 22672 164267011 Antolinc_Kris_-_Fotoredoks_arilacije_4-Okso-4H-piridino[1,2-a]pirimidin-3-diazonijevega_tetraflu.pdf Antolinc_Kris_-_Fotoredoks_arilacije_4-Okso-4H-piridino[1,2-a]pirimidin-3-diazonijevega_tetraflu.pdf 1 0F54668DC3CEF727285F2ECA3D1B3F04 685a2f150a6144f28acc02d81f6a17c5aeaae9d4ef7f254d06f43461e151441e 9b25318b-4d60-11ee-9934-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=174015 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0